Observed mechanism for the breakup of small bundles of cellulose Iα and Iβ in ionic liquids from molecular dynamics simulations.

PubMed

Rabideau, Brooks D; Agarwal, Animesh; Ismail, Ahmed E

2013-04-04

Explicit, all-atom molecular dynamics simulations are used to study the breakup of small bundles of cellulose Iα and Iβ in the ionic liquids [BMIM]Cl, [EMIM]Ac, and [DMIM]DMP. In all cases, significant breakup of the bundles is observed with the initial breakup following a common underlying mechanism. Anions bind strongly to the hydroxyl groups of the exterior strands of the bundle, forming negatively charged complexes. Binding also weakens the intrastrand hydrogen bonds present in the cellulose strands, providing greater strand flexibility. Cations then intercalate between the individual strands, likely due to charge imbalances, providing the bulk to push the individual moieties apart and initiating the separation. The peeling of an individual strand from the main bundle is observed in [EMIM]Ac with an analysis of its hydrogen bonds with other strands showing that the chain detaches glucan by glucan from the main bundle in discrete, rapid events. Further analysis shows that the intrastrand hydrogen bonds of each glucan tend to break for a sustained period of time before the interstrand hydrogen bonds break and strand detachment occurs. Examination of similar nonpeeling strands shows that, without this intrastrand hydrogen bond breakage, the structural rigidity of the individual unit can hinder its peeling despite interstrand hydrogen bond breakage.

Bond-orientational analysis of hard-disk and hard-sphere structures.

PubMed

Senthil Kumar, V; Kumaran, V

2006-05-28

We report the bond-orientational analysis results for the thermodynamic, random, and homogeneously sheared inelastic structures of hard-disks and hard-spheres. The thermodynamic structures show a sharp rise in the order across the freezing transition. The random structures show the absence of crystallization. The homogeneously sheared structures get ordered at a packing fraction higher than the thermodynamic freezing packing fraction, due to the suppression of crystal nucleation. On shear ordering, strings of close-packed hard-disks in two dimensions and close-packed layers of hard-spheres in three dimensions, oriented along the velocity direction, slide past each other. Such a flow creates a considerable amount of fourfold order in two dimensions and body-centered-tetragonal (bct) structure in three dimensions. These transitions are the flow analogs of the martensitic transformations occurring in metals due to the stresses induced by a rapid quench. In hard-disk structures, using the bond-orientational analysis we show the presence of fourfold order. In sheared inelastic hard-sphere structures, even though the global bond-orientational analysis shows that the system is highly ordered, a third-order rotational invariant analysis shows that only about 40% of the spheres have face-centered-cubic (fcc) order, even in the dense and near-elastic limits, clearly indicating the coexistence of multiple crystalline orders. When layers of close-packed spheres slide past each other, in addition to the bct structure, the hexagonal-close-packed (hcp) structure is formed due to the random stacking faults. Using the Honeycutt-Andersen pair analysis and an analysis based on the 14-faceted polyhedra having six quadrilateral and eight hexagonal faces, we show the presence of bct and hcp signatures in shear ordered inelastic hard-spheres. Thus, our analysis shows that the dense sheared inelastic hard-spheres have a mixture of fcc, bct, and hcp structures.

Influence of Etching Mode on Enamel Bond Durability of Universal Adhesive Systems.

PubMed

Suzuki, T; Takamizawa, T; Barkmeier, W W; Tsujimoto, A; Endo, H; Erickson, R L; Latta, M A; Miyazaki, M

2016-01-01

The purpose of this study was to determine the enamel bond durability of three universal adhesives in different etching modes through fatigue testing. The three universal adhesives used were Scotchbond Universal, Prime&Bond Elect universal dental adhesive, and All-Bond Universal light-cured dental adhesive. A single-step self-etch adhesive, Clearfil S 3 Bond Plus was used as a control. The shear bond strength (SBS) and shear fatigue strength (SFS) to human enamel were evaluated in total-etch mode and self-etch mode. A stainless steel metal ring with an internal diameter of 2.4 mm was used to bond the resin composite to the flat-ground (4000-grit) tooth surfaces for determination of both SBS and SFS. For each enamel surface treatment, 15 specimens were prepared for SBS and 30 specimens for SFS. The staircase method for fatigue testing was then used to determine the SFS of the resin composite bonded to the enamel using 10-Hz frequencies for 50,000 cycles or until failure occurred. Scanning electron microscopy was used to observe representative debonded specimen surfaces and the resin-enamel interfaces. A two-way analysis of variance and the Tukey post hoc test were used for analysis of the SBS data, whereas a modified t-test with Bonferroni correction was used for the SFS data. All adhesives in total-etch mode showed significantly higher SBS and SFS values than those in self-etch mode. Although All-Bond Universal in self-etch mode showed a significantly lower SBS value than the other adhesives, there was no significant difference in SFS values among the adhesives in this mode. All adhesives showed higher SFS:SBS ratios in total-etch mode than in self-etch mode. With regard to the adhesive systems used in this study, universal adhesives showed higher enamel bond strengths in total-etch mode. Although the influence of different etching modes on the enamel-bonding performance of universal adhesives was found to be dependent on the adhesive material, total-etch mode effectively increased the enamel bond strength and durability, as measured by fatigue testing.

Natural bond orbital analysis, electronic structure, non-linear properties and vibrational spectral analysis of L-histidinium bromide monohydrate: a density functional theory.

PubMed

Sajan, D; Joseph, Lynnette; Vijayan, N; Karabacak, M

2011-10-15

The spectroscopic properties of the crystallized nonlinear optical molecule L-histidinium bromide monohydrate (abbreviated as L-HBr-mh) have been recorded and analyzed by FT-IR, FT-Raman and UV techniques. The equilibrium geometry, vibrational wavenumbers and the first order hyperpolarizability of the crystal were calculated with the help of density functional theory computations. The optimized geometric bond lengths and bond angles obtained by using DFT (B3LYP/6-311++G(d,p)) show good agreement with the experimental data. The complete assignments of fundamental vibrations were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. The natural bond orbital (NBO) analysis confirms the occurrence of strong intra and intermolecular N-H⋯O hydrogen bonding. Copyright © 2011 Elsevier B.V. All rights reserved.

Room temperature bonding and debonding of polyimide film and glass substrate based on surface activate bonding method

NASA Astrophysics Data System (ADS)

Takeuchi, Kai; Fujino, Masahisa; Matsumoto, Yoshiie; Suga, Tadatomo

2018-02-01

The temporary bonding of polyimide (PI) films and glass substrates is a key technology for realizing flexible devices with thin-film transistors (TFTs). In this paper, we report the surface activated bonding (SAB) method using Si intermediate layers and its bonding and debonding mechanisms after heating. The bonding interface composed of Si and Fe shows a higher bond strength than the interface of only Si, while the bond strengths of both interfaces decrease with post bonding heating. It is also clarified by composition analysis on the debonded surfaces and cross-sectional observation of the bonding interface that the bond strength depends on the toughness of the intermediated layers and PI. The SAB method using Si intermediate layers is found to be applicable to the bonding and debonding of PI and glass.

The effect of antioxidant concentration of N-isopropyl-N-phenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline and mixing time of physical properties, thermal properties, mechanical properties and microstructure on natural rubber compound

NASA Astrophysics Data System (ADS)

Budiarto

2017-03-01

Study the influence of high concentrations of antioxidants N-isopropyl-N-phenyl-p-phenylenediamine (IPPD) and 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) and the mixing time of the vulcanization physical properties, thermal properties, mechanical properties and structure micro on natural rubber compound has been done. The purpose of this study is to compare the effect of anti-oxidants types IPPD and TMQ and mixing time of vulcanization of the physical properties, mechanical properties, microstructure and elemental composition of the synthesis of natural rubber compound. Processes of vulcanization with variations in the concentration of antioxidant IPPD and TMQ: 2, 3, and 4 grams and mixing time: 20, 30, and 40 minutes. Analysis characterization of physical properties and mechanical properties of natural rubber compound showed that the maturity value 0,499Nm (TMQ) and 0.489 Nm (IPPD), Mooney viscosity value of 26.7 (TMQ) and 20.8 (IPPD), the value of the elongation at break 583.75 % (IPPD), and 552.63% (TMQ) as well as the value of tensile strength of 28.108 M.Pa (TMQ), and 27.986 M.Pa (IPPD). Analysis of thermal properties of natural rubber compound antioxidant IPPD with DTA shows there are three endothermic peak on the curve that is temperature 405°C, 550°C and 660°C and tested by TGA showed that the curve of the total reduction in the sample are 81.745% and compound rubber antioxidant TMQ with the analysis of DTA also contained 3 endothermic peak at a temperature 397,21°C, 514,02°C, and 610,27°C and TGA analysis shows the curve of the total sample of 82.356% reduction. Gsi fun group analysis rubber-antioxidant compound IPPD / TMQ with FTIR spectrophotometer shows some typical infrared absorption peak at the wave number (1 / λ) 833-895 cm-1 for cluster / CH bonds, 1,313 cm-1 for group / single bond Si-O, 1368 cm-1 to g ugus / single bond CC, 1507 cm-1, for cluster / bond C = C, 1665 cm-1For cluster / bond-C = O, 2128 cm-1 is the group / bond CN single, 3371cm-1 for group-OH, 3506 cm-1 for cluster / CH3 bond and 3585 cm-1 showed the presence of vibration in the cluster / bond-NH. The results of morphological observation with SEM produces uneven surface (homogeneous) and are compatible at 2000 times magnification, as well as the test composition by EDX spectroscopy showed that the biggest element in the rubber compound is carbon and Zn, S, Ca, Si, Mg, Al, N. This shows that the natural rubber compound antioxidant IPPD / TMQ meet the standard of "Mechanical Properties of Industrial Tyre rubber Compounds".

Interpretation FTIR spectrum of seawater and sediment in the Ambon Bay (TAD)

NASA Astrophysics Data System (ADS)

Patty, Diana Julaidy; Loupatty, Grace; Sopalauw, Fitria

2017-01-01

Research has done to interpretated FTIR spectrum of seawaters and sediment of the Ambon Bay (TAD). Analysis of samples of sediment and seawater using FTIR spectroscopy. The results showed the sand sediment samples identified Stretch bond OH group (3600-3500 cm-1), N-H Stretch (3400-3300 cm-1), C≡N (2250 cm-1), and NH bending (1640 to 1550 cm-1). And for seawater samples identified bonding group that is N-H Stretch (3400-3350 cm-1), N-H bending (1640 to 1550 cm-1) and C=O (1670-1640 cm-1). The existence of functional groups, carbonyl (C=O), alcohol (OH), carboxyl (COOH) can cause the complexation of metal cations. And the results showed analysis group N-O bond-containing compounds Nitro indicate heavy metal content of Lead (Pb) and group N-H bond-containing compound Amina indicate heavy metal content of Cadmium (Cd).

Interconnect mechanisms in microelectronic packaging

NASA Astrophysics Data System (ADS)

Roma, Maria Penafrancia C.

Global economic, environmental and market developments caused major impact in the microelectronics industry. Astronomical rise of gold metal prices over the last decade shifted the use of copper and silver alloys as bonding wires. Environmental legislation on the restriction of the use of Pb launched worldwide search for lead-free solders and platings. Finally, electrical and digital uses demanded smaller, faster and cheaper devices. Ultra-fine pitch bonding, decreasing bond wire sizes and hard to bond substrates have put the once-robust stitch bond in the center of reliability issues due to stitch bond lift or open wires .Unlike the ball bond, stitch bonding does not lead to intermetallic compound formation but adhesion is dependent on mechanical deformation, interdiffusion, solid solution formation, void formation and mechanical interlocking depending on the wire material, bond configuration, substrate type , thickness and surface condition. Using Au standoff stitch bonds on NiPdAu plated substrates eliminated stitch bond lift even when the Au and Pd layers are reduced. Using the Matano-Boltzmann analysis on a STEM (Scanning Transmission Analysis) concentration profile the interdiffusion coefficient is measured to be 10-16 cm 2/s. Wire pull strength data showed that the wire pull strength is 0.062N and increases upon stress testing. Meanwhile, coating the Cu wire with Pd, not only increases oxidation resistance but also improved adhesion due to the formation of a unique interfacial adhesion layers. Adhesion strength as measured by pull showed the Cu wire bonded to Ag plated Cu substrate (0.132N) to be stronger than the Au wire bonded on the same substrate (0.124N). Ag stitch bonded to Au is predicted to be strong but surface modification made the adhesion stronger. However, on the Ag ball bonded to Al showed multiple IMC formation with unique morphology exposed by ion milling and backscattered scanning electron microscopy. Adding alloying elements in the Ag wire alloy showed differences in adhesion strength and IMC formation. Bond strength by wire pull testing showed the 95Ag alloy with higher values while shear bond testing showed the 88Ag higher bond strength. Use of Cu pillars in flip chips and eutectic bonding in wafer level chip scale packages are direct consequences of diminishing interconnect dimension as a result of the drive for miniaturization. The combination of Cu-Sn interdiffusion, Kirkendall mechanism and heterogeneous vacancy precipitation are the main causes of IMC and void formation in Cu pillar - Sn solder - Cu lead frame sandwich structure. However, adding a Ni barrier agent showed less porous IMC layer as well as void formation as a result of the modified Cu and Sn movement well as the void formation. Direct die to die bonding using Al-Ge eutectic bonds is necessary when 3D integration is needed to reduce the footprint of a package. Hermeticity and adhesion strength are a function of the Al/Ge thickness ratio, bonding pressure, temperature and time. Scanning Electron Microscope (SEM) and Focused Ion Beam (FIB) allowed imaging of interfacial microstructures, porosity, grain morphology while Scanning Transmission Electron microscope (STEM) provided diffusion profile and confirmed interdiffusion. Ion polishing technique provided information on porosity and when imaged using backscattered mode, grain structure confirmed mechanical deformation of the bonds. Measurements of the interfacial bond strength are made by wire pull tests and ball shear tests based on existing industry standard tests. However, for the Al-Ge eutectic bonds, no standard strength is available so a test is developed using the stud pull test method using the Dage 4000 Plus to yield consistent results. Adhesion strengths of 30-40 MPa are found for eutectic bonded packages however, as low as 20MPa was measured in low temperature bonded areas.

Analysis of bonded joints. [shear stress and stress-strain diagrams

NASA Technical Reports Server (NTRS)

Srinivas, S.

1975-01-01

A refined elastic analysis of bonded joints which accounts for transverse shear deformation and transverse normal stress was developed to obtain the stresses and displacements in the adherends and in the bond. The displacements were expanded in terms of polynomials in the thicknesswise coordinate; the coefficients of these polynomials were functions of the axial coordinate. The stress distribution was obtained in terms of these coefficients by using strain-displacement and stress-strain relations. The governing differential equations were obtained by integrating the equations of equilibrium, and were solved. The boundary conditions (interface or support) were satisfied to complete the analysis. Single-lap, flush, and double-lap joints were analyzed, along with the effects of adhesive properties, plate thicknesses, material properties, and plate taper on maximum peel and shear stresses in the bond. The results obtained by using the thin-beam analysis available in the literature were compared with the results obtained by using the refined analysis. In general, thin-beam analysis yielded reasonably accurate results, but in certain cases the errors were high. Numerical investigations showed that the maximum peel and shear stresses in the bond can be reduced by (1) using a combination of flexible and stiff bonds, (2) using stiffer lap plates, and (3) tapering the plates.

Molecular and electronic structures of M 2O 7 (M = Mn, Tc, Re)

DOE PAGES

Lawler, Keith V.; Childs, Bradley C.; Mast, Daniel S.; ...

2017-02-21

The molecular and electronic structures for the Group 7b heptoxides were investigated by computational methods as both isolated molecules and in the solid-state. The metal-oxygen-metal bending angle of the single molecule increased with increasing atomic number, with Re 2O 7 preferring a linear structure. Natural bond orbital and localized orbital bonding analyses indicate that there is a three-center covalent bond between the metal atoms and the bridging oxygen, and the increasing ionic character of the bonds favors larger bond angles. The calculations accurately reproduce the experimental crystal structures within a few percent. Analysis of the band structures and density ofmore » states shows similar bonding for all of the solid-state heptoxides, including the presence of the three-center covalent bond. DFT+U simulations show that PBE-D3 underpredicts the band gap by ~0.2 eV due to an under-correlation of the metal d conducting states. As a result, homologue and compression studies show that Re 2O 7 adopts a polymeric structure because the Re-oxide tetrahedra are easily distorted by packing stresses to form additional three-center covalent bonds.« less

Evaluation of microtensile and tensile bond strength tests determining effects of erbium, chromium: yttrium-scandium-gallium-garnet laser pulse frequency on resin-enamel bonding.

PubMed

Yildirim, T; Ayar, M K; Yesilyurt, C; Kilic, S

2016-01-01

The aim of the present study was to compare two different bond strength test methods (tensile and microtensile) in investing the influence of erbium, chromium: yttrium-scandium-gallium-garnet (Er, Cr: YSGG) laser pulse frequency on resin-enamel bonding. One-hundred and twenty-five bovine incisors were used in the present study. Two test methods were used: Tensile bond strength (TBS; n = 20) and micro-TBS (μTBS; n = 5). Those two groups were further split into three subgroups according to Er, Cr: YSGG laser frequency (20, 35, and 50 Hz). Following adhesive procedures, microhybrid composite was placed in a custom-made bonding jig for TBS testing and incrementally for μTBS testing. TBS and μTBS tests were carried out using a universal testing machine and a microtensile tester, respectively. Analysis of TBS results showed that means were not significantly different. For μTBS, the Laser-50 Hz group showed the highest bond strength (P < 0.05), and increasing frequency significantly increased bond strength (P < 0.05). Comparing the two tests, the μTBS results showed higher means and lower standard deviations. It was demonstrated that increasing μTBS pulse frequency significantly improved immediate bond strength while TBS showed no significant effect. It can, therefore, be concluded that test method may play a significant role in determining optimum laser parameters for resin bonding.

Effect of metal conditioner on bonding of porcelain to cobalt-chromium alloy

PubMed Central

Kajihara, Yutaro; Takenouchi, Yoshihisa; Tanaka, Takuo; Suzuki, Shiro; Minami, Hiroyuki

2016-01-01

PURPOSE The purpose of this study was to evaluate the efficacy of two different metal conditioners for non-precious metal alloys for the bonding of porcelain to a cobalt-chromium (Co-Cr) alloy. MATERIALS AND METHODS Disk-shaped specimens (2.5×10.0 mm) were cast with Co-Cr alloy and used as adherend materials. The bonding surfaces were polished with a 600-grid silicon carbide paper and airborne-particle abraded using 110 µm alumina particles. Bonding specimens were fabricated by applying and firing either of the metal conditioners on the airborne-particle abraded surface, followed by firing porcelain into 5 mm in diameter and 3 mm in height. Specimens without metal conditioner were also fabricated. Shear bond strength for each group (n=8) were measured and compared (α=.05). Sectional view of bonding interface was observed by SEM. EDS analysis was performed to determine the chemical elements of metal conditioners and to determine the failure modes after shear test. RESULTS There were significant differences among three groups, and two metal conditioner-applied groups showed significantly higher values compared to the non-metal conditioner group. The SEM observation of the sectional view at bonding interface revealed loose contact at porcelain-alloy surface for non-metal conditioner group, however, close contact at both alloy-metal conditioner and metal conditioner-porcelain interfaces for both metal conditioner-applied groups. All the specimens showed mixed failures. EDS analysis showed that one metal conditioner was Si-based material, and another was Ti-based material. Si-based metal conditioner showed higher bond strengths compared to the Ti-based metal conditioner, but exhibited more porous failure surface failure. CONCLUSION Based on the results of this study, it can be stated that the application of metal conditioner is recommended for the bonding of porcelain to cobalt-chromium alloys. PMID:26949481

A study on the compatibility between one-bottle dentin adhesives and composite resins using micro-shear bond strength.

PubMed

Song, Minju; Shin, Yooseok; Park, Jeong-Won; Roh, Byoung-Duck

2015-02-01

This study was performed to determine whether the combined use of one-bottle self-etch adhesives and composite resins from same manufacturers have better bond strengths than combinations of adhesive and resins from different manufacturers. 25 experimental micro-shear bond test groups were made from combinations of five dentin adhesives and five composite resins with extracted human molars stored in saline for 24 hr. Testing was performed using the wire-loop method and a universal testing machine. Bond strength data was statistically analyzed using two way analysis of variance (ANOVA) and Tukey's post hoc test. Two way ANOVA revealed significant differences for the factors of dentin adhesives and composite resins, and significant interaction effect (p < 0.001). All combinations with Xeno V (Dentsply De Trey) and Clearfil S(3) Bond (Kuraray Dental) adhesives showed no significant differences in micro-shear bond strength, but other adhesives showed significant differences depending on the composite resin (p < 0.05). Contrary to the other adhesives, Xeno V and BondForce (Tokuyama Dental) had higher bond strengths with the same manufacturer's composite resin than other manufacturer's composite resin. Not all combinations of adhesive and composite resin by same manufacturers failed to show significantly higher bond strengths than mixed manufacturer combinations.

Transition joints between Zircaloy-2 and stainless steel by diffusion bonding

NASA Astrophysics Data System (ADS)

Bhanumurthy, K.; Krishnan, J.; Kale, G. B.; Banerjee, S.

1994-11-01

The diffusion bonding between Zircaloy-2 and stainless steel (AISI 304L) using niobium, nickel and copper as intermediate layers has been investigated in the temperature range of 750 to 900°C. Bonding was carried out in a vacuum hot press, under compressive loading. Electron probe microanalysis and metallographic analysis showed a good metallurgical compatibility and also indicated the absence of discontunities, micropores and intermetallic compounds at various interfaces. The bond strength of the diffusion bonded assembly was found to be about 400 MPa for the couples bonded at 870°C for 2 h. The dimple structure on the fractured surface is indicative of the ductile mode of failure of the bonded assembly.

A new class of halogen bonds that avoids the σ-hole

NASA Astrophysics Data System (ADS)

Zhang, Yu; Ma, Ning; Wang, Weizhou

2012-04-01

A new class of halogen bonds of the type X = Hal⋯Y has been investigated by using the density functional theory calculations. The strength of this new class of halogen bonds is in the range of 90-120 kcal/mol, which is greatly larger than that of the conventional halogen bond of the type X-Hal⋯Y. The geometry of this new class of halogen bonds is not determined by the halogen's positive σ-hole. Natural bond orbital analysis shows it is the n → π∗ interaction that determines the geometry of this new class of halogen bonds. Experimental results are in good agreement with the theoretical predictions.

Influence of PNA containing 8-aza-7-deazaadenine on structure stability and binding affinity of PNA·DNA duplex: insights from thermodynamics, counter ion, hydration and molecular dynamics analysis.

PubMed

Gupta, Sharad K; Sur, Souvik; Prasad Ojha, Rajendra; Tandon, Vibha

2013-07-01

This paper describes the synthesis of a novel 8-aza-7-deazapurin-2,6-diamine (DPP)-containing peptide nucleic acid (PNA) monomer and Boc protecting group-based oligomerization of PNA, replacing adenine (A) with DPP monomers in the PNA strand. The PNA oligomers were synthesized against the biologically relevant SV40 promoter region (2494-AATTTTTTTTATTTA-2508) of pEGFP-N3 plasmid. The DPP-PNA·DNA duplex showed enhanced stability as compared to normal duplex (A-PNA·DNA). The electronic distribution of DPP monomer suggested that DPP had better electron donor properties over 2,6-diamino purine. UV melting and thermodynamic analysis revealed that the PNA oligomer containing a diaminopyrazolo(3,4-d)pyrimidine moiety (DPP) stabilized the PNA·DNA hybrids compared to A-PNA·DNA. DPP-PNA·DNA duplex showed higher water activity (Δnw = 38.5) in comparison to A-PNA·DNA duplex (Δnw = 14.5). The 50 ns molecular dynamics simulations of PNA·DNA duplex containing DPP or unmodified nucleobase-A showed average H-bond distances in the DPP-dT base pair of 2.90 Å (OH-N bond) and 2.91 Å (NH-N bond), which were comparably shorter than in the A-dT base pair, in which the average distances were 3.18 Å (OH-N bond) and 2.97 Å (NH-N bond), and there was one additional H-bond in the DPP-dT base pair of around 2.98 Å (O2H-N2 bond), supporting the higher stability of DPP-PNA·DNA. The analysis of molecular dynamics simulation data showed that the system binding free energy increased at a rate of approximately -4.5 kcal mol(-1) per DPP base of the PNA·DNA duplex. In summary, increased thermal stability, stronger hydrogen bonding and more stable conformation in the DPP-PNA·DNA duplex make it a better candidate as antisense/antigene therapeutic agents.

Characterization of the hydrogen-bond network of water around sucrose and trehalose: H-O-H bending analysis

NASA Astrophysics Data System (ADS)

Shiraga, Keiichiro; Adachi, Aya; Ogawa, Yuichi

2017-06-01

The bioprotective properties of disaccharides have been linked to destructuring effect on the hydrogen-bond structure of the interfacial water around the disaccharide solute, but its detailed mechanisms are yet to be provided. In this study, we characterized the destructuring effect based on the complex dielectric constants of interfacial water around sucrose and trehalose in the H-O-H bending region. Our analysis showed that the destructuring effect around disaccharides involves substantial disordering of the hydrogen-bond structure and formation of strong disaccharide-water hydrogen-bond. Such a destructuring effect caused by disaccharides is totally distinct from what happens with temperature increases of neat water.

Theoretical and Experimental Studies on the Nonlinear Optical Chromophore para Bromoacetanilide

NASA Astrophysics Data System (ADS)

Jothy, V. Bena; Vijayakumar, T.; Jayakumar, V. S.; Udayalekshmi, K.; Ramamurthy, K.; Joe, I. Hubert

2008-11-01

Vibrational spectral analysis of the hydrogen bonded non-linear optical (NLO) material para Bromo Acetanilide (PBA) is carried out using NIR FT-Raman and FT-IR spectroscopy. Ab initio molecular orbital computations have been performed at HF/6-31G(d) level to derive equilibrium geometry, vibrational wavenumbers, intensities and first hyperpolarizability. The lowering of the imino stretching wavenumbers suggests the existence of strong intermolecular N-H⋯O hydrogen bonding substantiated by the natural bond orbital (NBO) analysis. Blue shifting CH stretching wavenumbers, simultaneous activation of carbonyl stretching mode and the strong activation of low wavenumber H-bond stretching vibrations shows the presence of intramolecular charge transfer in the molecule.

The two faces of hydrogen-bond strength on triple AAA-DDD arrays.

PubMed

Lopez, Alfredo Henrique Duarte; Caramori, Giovanni Finoto; Coimbra, Daniel Fernando; Parreira, Renato Luis Tame; da Silva, Éder Henrique

2013-12-02

Systems that are connected through multiple hydrogen bonds are the cornerstone of molecular recognition processes in biology, and they are increasingly being employed in supramolecular chemistry, specifically in molecular self-assembly processes. For this reason, the effects of different substituents (NO2, CN, F, Cl, Br, OCH3 and NH2) on the electronic structure, and consequently on the magnitude of hydrogen bonds in triple AAA-DDD arrays (A=acceptor, D=donor) were evaluated in the light of topological [electron localization function (ELF) and quantum theory of atoms in molecules (QTAIM)], energetic [Su-Li energy-decomposition analysis (EDA) and natural bond orbital analysis (NBO)], and geometrical analysis. The results based on local H-bond descriptors (geometries, QTAIM, ELF, and NBO) indicate that substitutions with electron-withdrawing groups on the AAA module tend to strengthen, whereas electron-donating substituents tend to weaken the covalent character of the AAA-DDD intermolecular H-bonds, and also indicate that the magnitude of the effect is dependent on the position of substitution. In contrast, Su-Li EDA results show an opposite behavior when compared to local H-bond descriptors, indicating that electron-donating substituents tend to increase the magnitude of H-bonds in AAA-DDD arrays, and thus suggesting that the use of local H-bond descriptors describes the nature of H bonds only partially, not providing enough insight about the strength of such H bonds. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recrystallization characteristics and interfacial oxides on the compression bonding interface

NASA Astrophysics Data System (ADS)

Xie, Bijun; Sun, Mingyue; Xu, Bin; Li, Dianzhong

2018-05-01

Up to now, the mechanism of interface bonding is still not fully understood. This work presents interfacial characteristics of 316LN stainless steel bonding joint after cold compression bonding with subsequent annealing. EBSD analysis shows that fine recrystallization grains preferentially appear near the bonding interface and grow towards both sides of the interface. Transmission electron microscopy reveals that initial cold compression bonding disintegrates the native oxide scales and brings pristine metal from both sides of the interface come into intimate contact, while the broken oxide particles are remained at the original interface. The results indicate that partial bonding can be achieved by cold compression bonding with post-annealing treatment and recrystallization firstly occurs along the bonding interface. However, the interfacial oxides impede the recrystallization grains step over the interface and hinder the complete healing of the bonding interface.

Bond strength comparison of 2 self-etching primers over a 3-month storage period.

PubMed

Trites, Brian; Foley, Timothy F; Banting, David

2004-12-01

The purpose of this in vitro study was to evaluate the shear-peel bond strength of 2 self-etching primer systems, Transbond Plus (3M/ Unitek, Monrovia, Calif) and First Step (Reliance Orthodontic Products, Itasca, Ill), with their respective adhesives, and compare them with a control adhesive system (Transbond XT, 3M/ Unitek) over a 3-month period. Two hundred seventy extracted human premolars were obtained and randomly divided into 9 groups of 30 teeth. Metal orthodontic brackets were bonded to the enamel, and each adhesive group was stored for 24 horrs (T1), 30 days (T2), or 3 months (T3) in deionized water at 37 degrees C. All bonded specimens were thermocycled at 10 degrees C and 50 degrees C for 24 hours before debonding. Brackets were debonded by using a shear-peel load on a testing machine at a cross-head speed of 2 mm/min. Bond failure was also evaluated. The shear-peel bond strengths of the 3 bonding systems were clinically acceptable with the possible exception of First Step at 30-day storage. Repeated measures analysis of variance showed a statistically significant (P < .0001) difference in mean bond strengths between the 3 adhesive systems. The shear-peel bond strength of the adhesives over the 3 time intervals showed statistically significant (P = .005) changes. In each group, there were statistically significant differences in shear-peel bond strength between time intervals T1-T2 and T2-T3 for Transbond Plus and T2-T3 for First Step. The change in mean shear-peel bond strength of the 3 adhesives demonstrated a consistent pattern of behavior over the 3 storage intervals. The lowest mean shear-peel bond strength values were noted at the 30-day storage. Bond failure analysis (adhesive remnant index) demonstrated mainly cohesive bond failures.

Do Halogen–Hydrogen Bond Donor Interactions Dominate the Favorable Contribution of Halogens to Ligand–Protein Binding?

PubMed Central

2017-01-01

Halogens are present in a significant number of drugs, contributing favorably to ligand–protein binding. Currently, the contribution of halogens, most notably chlorine and bromine, is largely attributed to halogen bonds involving favorable interactions with hydrogen bond acceptors. However, we show that halogens acting as hydrogen bond acceptors potentially make a more favorable contribution to ligand binding than halogen bonds based on quantum mechanical calculations. In addition, bioinformatics analysis of ligand–protein crystal structures shows the presence of significant numbers of such interactions. It is shown that interactions between halogens and hydrogen bond donors (HBDs) are dominated by perpendicular C–X···HBD orientations. Notably, the orientation dependence of the halogen–HBD (X–HBD) interactions is minimal over greater than 100° with favorable interaction energies ranging from −2 to −14 kcal/mol. This contrasts halogen bonds in that X–HBD interactions are substantially more favorable, being comparable to canonical hydrogen bonds, with a smaller orientation dependence, such that they make significant, favorable contributions to ligand–protein binding and, therefore, should be actively considered during rational ligand design. PMID:28657759

Multiple hydrogen-bonded complexes based on 2-ureido-4[1H]-pyrimidinone: a theoretical study.

PubMed

Sun, Hao; Lee, Hui Hui; Blakey, Idriss; Dargaville, Bronwin; Chirila, Traian V; Whittaker, Andrew K; Smith, Sean C

2011-09-29

In the present work, the electronic structures and properties of a series of 2-ureido-4[1H]-pyrimidinone(UPy)-based monomers and dimers in various environments (vacuum, chloroform, and water) are studied by density functional theoretical methods. Most dimers prefer to form a DDAA-AADD (D, H-bond donor; A, H-bond acceptor) array in both vacuum and solvents. Topological analysis proved that intramolecular and intermolecular hydrogen bonds coexist in the dimers. Frequency and NBO calculations show that all the hydrogen bonds exhibit an obvious red shift in their stretching vibrational frequencies. Larger substituents at position 6 of the pyrimidinone ring with stronger electron-donating ability favor the total binding energy and free energy of dimerization. Calculations on the solvent effect show that dimerization is discouraged by the stronger polarity of the solvent. Further computations show that Dimer-1 may be formed in chloroform, but water molecules may interact with the donor or acceptor sites and hence disrupt the hydrogen bonds of Dimer-1. © 2011 American Chemical Society

Unusually short chalcogen bonds involving organoselenium: insights into the Se-N bond cleavage mechanism of the antioxidant ebselen and analogues.

PubMed

Thomas, Sajesh P; Satheeshkumar, K; Mugesh, Govindasamy; Guru Row, T N

2015-04-27

Structural studies on the polymorphs of the organoselenium antioxidant ebselen and its derivative show the potential of organic selenium to form unusually short Se⋅⋅⋅O chalcogen bonds that lead to conserved supramolecular recognition units. Se⋅⋅⋅O interactions observed in these polymorphs are the shortest such chalcogen bonds known for organoselenium compounds. The FTIR spectral evolution characteristics of this interaction from solution state to solid crystalline state further validates the robustness of this class of supramolecular recognition units. The strength and electronic nature of the Se⋅⋅⋅O chalcogen bonds were explored using high-resolution X-ray charge density analysis and atons-in-molecules (AIM) theoretical analysis. A charge density study unravels the strong electrostatic nature of Se⋅⋅⋅O chalcogen bonding and soft-metal-like behavior of organoselenium. An analysis of the charge density around Se-N and Se-C covalent bonds in conjunction with the Se⋅⋅⋅O chalcogen bonding modes in ebselen and its analogues provides insights into the mechanism of drug action in this class of organoselenium antioxidants. The potential role of the intermolecular Se⋅⋅⋅O chalcogen bonding in forming the intermediate supramolecular assembly that leads to the bond cleavage mechanism has been proposed in terms of electron density topological parameters in a series of molecular complexes of ebselen with reactive oxygen species (ROS). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

FT-IR and Raman spectra, DFT and SQMFF calculations for geometrical interpretation and vibrational analysis of 3-nitro-p-toluic acid

NASA Astrophysics Data System (ADS)

Nataraj, A.; Balachandran, V.; Karthick, T.

2012-08-01

The Fourier transform infrared (FT-IR) and FT-Raman of 3-nitro-p-toluic acid (NTA) have been recorded and analyzed. The equilibrium geometry, bonding features and harmonic vibrational frequencies have been investigated with the help of ab initio and density functional theory (DFT) methods. The assignments of the vibrational spectra have been carried out with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFF). The optimized geometric bond lengths and bond angles obtained by computation show good agreement with experimental data of the relative compound. The computed dimer parameters also show good agreement with experimental data. The first hyperpolarizability (β0) of this noval molecular system and related properties (β, α0, and Δα) of NTA are calculated using B3LYP/6-311++G(d,p) method on the finite-field approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ* and π* antibonding orbital and second order delocalization energies E(2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The calculated HOMO and LUMO energies also show that charge transfer occurs within the molecule. Finally the calculations results were applied to simulated infrared and Raman spectra of the title compound which show good agreement with observed spectra.

New insights into the folding of a β-sheet miniprotein in a reduced space of collective hydrogen bond variables: application to a hydrodynamic analysis of the folding flow.

PubMed

Kalgin, Igor V; Caflisch, Amedeo; Chekmarev, Sergei F; Karplus, Martin

2013-05-23

A new analysis of the 20 μs equilibrium folding/unfolding molecular dynamics simulations of the three-stranded antiparallel β-sheet miniprotein (beta3s) in implicit solvent is presented. The conformation space is reduced in dimensionality by introduction of linear combinations of hydrogen bond distances as the collective variables making use of a specially adapted principal component analysis (PCA); i.e., to make structured conformations more pronounced, only the formed bonds are included in determining the principal components. It is shown that a three-dimensional (3D) subspace gives a meaningful representation of the folding behavior. The first component, to which eight native hydrogen bonds make the major contribution (four in each beta hairpin), is found to play the role of the reaction coordinate for the overall folding process, while the second and third components distinguish the structured conformations. The representative points of the trajectory in the 3D space are grouped into conformational clusters that correspond to locally stable conformations of beta3s identified in earlier work. A simplified kinetic network based on the three components is constructed, and it is complemented by a hydrodynamic analysis. The latter, making use of "passive tracers" in 3D space, indicates that the folding flow is much more complex than suggested by the kinetic network. A 2D representation of streamlines shows there are vortices which correspond to repeated local rearrangement, not only around minima of the free energy surface but also in flat regions between minima. The vortices revealed by the hydrodynamic analysis are apparently not evident in folding pathways generated by transition-path sampling. Making use of the fact that the values of the collective hydrogen bond variables are linearly related to the Cartesian coordinate space, the RMSD between clusters is determined. Interestingly, the transition rates show an approximate exponential correlation with distance in the hydrogen bond subspace. Comparison with the many published studies shows good agreement with the present analysis for the parts that can be compared, supporting the robust character of our understanding of this "hydrogen atom" of protein folding.

Effect of Airborne Particle Abrasion on Microtensile Bond Strength of Total-Etch Adhesives to Human Dentin

PubMed Central

Piccioni, Chiara; Di Carlo, Stefano; Capogreco, Mario

2017-01-01

Aim of this study was to investigate a specific airborne particle abrasion pretreatment on dentin and its effects on microtensile bond strengths of four commercial total-etch adhesives. Midcoronal occlusal dentin of extracted human molars was used. Teeth were randomly assigned to 4 groups according to the adhesive system used: OptiBond FL (FL), OptiBond Solo Plus (SO), Prime & Bond (PB), and Riva Bond LC (RB). Specimens from each group were further divided into two subgroups: control specimens were treated with adhesive procedures; abraded specimens were pretreated with airborne particle abrasion using 50 μm Al2O3 before adhesion. After bonding procedures, composite crowns were incrementally built up. Specimens were sectioned perpendicular to adhesive interface to produce multiple beams, which were tested under tension until failure. Data were statistically analysed. Failure mode analysis was performed. Overall comparison showed significant increase in bond strength (p < 0.001) between abraded and no-abraded specimens, independently of brand. Intrabrand comparison showed statistical increase when abraded specimens were tested compared to no-abraded ones, with the exception of PB that did not show such difference. Distribution of failure mode was relatively uniform among all subgroups. Surface treatment by airborne particle abrasion with Al2O3 particles can increase the bond strength of total-etch adhesives. PMID:29392128

Influence of ageing on self-etch adhesives: one-step vs. two-step systems.

PubMed

Marchesi, Giulio; Frassetto, Andrea; Visintini, Erika; Diolosà, Marina; Turco, Gianluca; Salgarello, Stefano; Di Lenarda, Roberto; Cadenaro, Milena; Breschi, Lorenzo

2013-02-01

The aim of this study was to evaluate microtensile bond strength (μTBS) to dentine, interfacial nanoleakage expression, and stability after ageing, of two-step vs. one-step self-etch adhesives. Human molars were cut to expose middle/deep dentine, assigned to groups (n = 15), and treated with the following bonding systems: (i) Optibond XTR (a two-step self-etch adhesive; Kerr), (ii) Clearfil SE Bond (a two-step self-etch adhesive; Kuraray), (iii) Adper Easy Bond (a one-step self-etch adhesive; 3M ESPE), and (iv) Bond Force (a one-step self-etch adhesive; Tokuyama). Specimens were processed for μTBS testing after 24 h, 6 months, or 1 yr of storage in artificial saliva at 37°C. Nanoleakage expression was examined in similarly processed additional specimens. At baseline the μTBS results ranked in the following order: Adper Easy Bond = Optibond XTR ≥Clearfil SE = Bond Force, and interfacial nanoleakage analysis showed Clearfil SE Bond = Adper Easy Bond = Optibond XTR> Bond Force. After 1 yr of storage, Optibond XTR, Clearfil SE Bond, and Adper Easy Bond showed higher μTBS and lower interfacial nanoleakage expression compared with Bond Force. In conclusion, immediate bond strength, nanoleakage expression, and stability over time were not related to the number of steps of the bonding systems, but to their chemical formulations. © 2012 Eur J Oral Sci.

Molecular structure, Normal Coordinate Analysis, harmonic vibrational frequencies, Natural Bond Orbital, TD-DFT calculations and biological activity analysis of antioxidant drug 7-hydroxycoumarin

NASA Astrophysics Data System (ADS)

Sebastian, S.; Sylvestre, S.; Jayarajan, D.; Amalanathan, M.; Oudayakumar, K.; Gnanapoongothai, T.; Jayavarthanan, T.

2013-01-01

In this work, we report harmonic vibrational frequencies, molecular structure, NBO and HOMO, LUMO analysis of Umbelliferone also known as 7-hydroxycoumarin (7HC). The optimized geometric bond lengths and bond angles obtained by computation (monomer and dimmer) shows good agreement with experimental XRD data. Harmonic frequencies of 7HC were determined and analyzed by DFT utilizing 6-311+G(d,p) as basis set. The assignments of the vibrational spectra have been carried out with the help of Normal Coordinate Analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). The change in electron density (ED) in the σ* and π* antibonding orbitals and stabilization energies E(2) have been calculated by Natural Bond Orbital (NBO) analysis to give clear evidence of stabilization originating in the hyperconjugation of hydrogen-bonded interaction. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) complements with the experimental findings. The simulated spectra satisfactorily coincides with the experimental spectra. Microbial activity of studied compounds was tested against Staphylococcus aureus, Streptococcus pyogenes, Bacillus subtilis, Escherichia coli, Psuedomonas aeruginosa, Klebsiella pneumoniae, Proteus mirabilis, Shigella flexneri, Salmonella typhi and Enterococcus faecalis.

Hydrogen bond and halogen bond inside the carbon nanotube

NASA Astrophysics Data System (ADS)

Wang, Weizhou; Wang, Donglai; Zhang, Yu; Ji, Baoming; Tian, Anmin

2011-02-01

The hydrogen bond and halogen bond inside the open-ended single-walled carbon nanotubes have been investigated theoretically employing the newly developed density functional M06 with the suitable basis set and the natural bond orbital analysis. Comparing with the hydrogen or halogen bond in the gas phase, we find that the strength of the hydrogen or halogen bond inside the carbon nanotube will become weaker if there is a larger intramolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom donor to the antibonding orbital of the X-H or X-Hal bond involved in the formation of the hydrogen or halogen bond and will become stronger if there is a larger intermolecular electron-density transfer from the electron-rich region of the hydrogen or halogen atom acceptor to the antibonding orbital of the X-H or X-Hal bond. According to the analysis of the molecular electrostatic potential of the carbon nanotube, the driving force for the electron-density transfer is found to be the negative electric field formed in the carbon nanotube inner phase. Our results also show that the X-H bond involved in the formation of the hydrogen bond and the X-Hal bond involved in the formation of the halogen bond are all elongated when encapsulating the hydrogen bond and halogen bond within the carbon nanotube, so the carbon nanotube confinement may change the blue-shifting hydrogen bond and the blue-shifting halogen bond into the red-shifting hydrogen bond and the red-shifting halogen bond. The possibility to replace the all electron nanotube-confined calculation by the simple polarizable continuum model is also evaluated.

Influence of metal bonding layer on strain transfer performance of FBG

NASA Astrophysics Data System (ADS)

Liu, Hao; Chen, Weimin; Zhang, Peng; Liu, Li; Shu, Yuejie; Wu, Jun

2013-01-01

Metal bonding layer seriously affects the strain transfer performance of Fiber Bragg Grating (FBG). Based on the mode of FBG strain transfer, the influence of the length, the thickness, Poisson's ratio, elasticity modulus of metal bonding layer on the strain transfer coefficient of FBG is analyzed by numerical simulation. FBG is packaged to steel wire using metal bonding technology of FBG. The tensile tests of different bonding lengths and elasticity modulus are carried out. The result shows the strain transfer coefficient of FBGs are 0.9848,0.962 and their average strain sensitivities are 1.076 pm/μɛ,1.099 pm/μɛ when the metal bonding layer is zinc, whose lengths are 15mm, 20mm, respectively. The strain transfer coefficient of FBG packaged by metal bonding layer raises 8.9 percent compared to epoxy glue package. The preliminary experimental results show that the strain transfer coefficient increases with the length of metal bonding layer, decreases with the thickness of metal bonding layer and the influence of Poisson's ratio can be ignored. The experiment result is general agreement with the analysis and provides guidance for metal package of FBG.

Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol.

PubMed

Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

2016-12-30

Amides are important atmospheric organic-nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N -methylformamide, N , N -dimethylformamide, acetamide, N -methylacetamide and N , N -dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH-amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O-H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol

PubMed Central

Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

2016-01-01

Amides are important atmospheric organic–nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide and N,N-dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH–amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O–H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components. PMID:28042825

Congruence of therapeutic bond perceptions and its relation to treatment outcome: Within- and between-dyad effects.

PubMed

Rubel, Julian A; Bar-Kalifa, Eran; Atzil-Slonim, Dana; Schmidt, Sebastian; Lutz, Wolfgang

2018-04-01

The present study investigates the association between congruence of patients' and therapists' perceptions of the therapeutic bond and symptom improvement. Bond congruence-outcome associations were examined on the within- and between-dyad level for 580 patients (mainly depression and anxiety) receiving cognitive-behavioral therapy. Symptom change was assessed on a session-to-session level as well as from pre- to posttreatment. For the between-dyad analyses, the truth and bias model was applied. For the within-dyad analyses, polynomial regression and response surface analysis were conducted. On the between-dyad level, higher temporal congruence between patients' and therapists' bond ratings (i.e., their correlation) was associated with better treatment outcomes. Additionally, the average discrepancy between therapists' and patients' bond ratings showed a significant quadratic association with treatment outcome. A tendency for therapists to moderately rate the bond lower than their patients' showed lowest posttreatment symptom scores. On the within-dyad level, we found that when patients' and therapists' ratings were in "agreement," higher bond scores were associated with fewer next-session symptoms. For "disagreement," the results showed that if therapists rated the bond as weak, whereas their patients rated it as strong, higher subsequent symptom distress was observed than if patients rated the bond as weak and their therapists rated it as strong. The present study highlights the importance of therapists being vigilant to session-to-session changes in the therapeutic bond to adjust their interventions accordingly. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Enamel Wetness Effects on Microshear Bond Strength of Different Bonding Agents (Adhesive Systems): An in vitro Comparative Evaluation Study.

PubMed

Kulkarni, Girish; Mishra, Vinay K

2016-05-01

The purpose of this study was to compare the effect of enamel wetness on microshear bond strength using different adhesive systems. To evaluate microshear bond strength of three bonding agents on dry enamel; to evaluate microshear bond strength of three bonding agents on wet enamel; and to compare microshear bond strength of three different bonding agents on dry and wet enamel. Sixty extracted noncarious human premolars were selected for this study. Flat enamel surfaces of approximately 3 mm were obtained by grinding the buccal surfaces of premolars with water-cooled diamond disks. This study evaluated one etch-and-rinse adhesive system (Single Bond 2) and two self-etching adhesive systems (Clearfil SE Bond and Xeno-V). The specimens were divided into two groups (n = 30). Group I (dry) was air-dried for 30 seconds and in group II (wet) surfaces were blotted with absorbent paper to remove excess water. These groups were further divided into six subgroups (n = 10) according to the adhesives used. The resin composite, Filtek Z 250, was bonded to flat enamel surfaces that had been treated with one of the adhesives, following the manufacturer's instructions. After being stored in water at 37°C for 24 hours, bonded specimens were stressed in universal testing machine (Fig. 3) at a crosshead speed of 1 mm/min. The data were evaluated with one-way and two-way analysis of variance (ANOVA), t-test, and Tukey's Multiple Post hoc tests (a = 0.05). The two-way ANOVA and Tukey's Multiple Post hoc tests showed significant differences among adhesive systems, but wetness did not influence microshear bond strength (p = 0.1762). The one-way ANOVA and t-test showed that the all-in-one adhesive (Xeno-V) was the only material influenced by the presence of water on the enamel surface. Xeno-V showed significantly higher microshear bond strength when the enamel was kept wet. Single Bond 2 adhesive showed significantly higher microshear bond strength as compared with Xeno-V adhesive but no significant difference when compared with Clearfil SE Bond adhesive in dry enamel. Single Bond 2 adhesive showed no significant difference in microshear bond strength as compared with self-etching adhesive systems (Clearfil SE Bond and Xeno-V), when the enamel was kept wet. From the findings of the results, it was concluded that self-etching adhesives were not negatively affected by the presence of water on the enamel surface. The all-in-one adhesive showed different behavior depending on whether the enamel surface was dry or wet. So the enamel surface should not be desiccated, when self-etching adhesives are used.

An HMM-based algorithm for evaluating rates of receptor–ligand binding kinetics from thermal fluctuation data

PubMed Central

Ju, Lining; Wang, Yijie Dylan; Hung, Ying; Wu, Chien-Fu Jeff; Zhu, Cheng

2013-01-01

Motivation: Abrupt reduction/resumption of thermal fluctuations of a force probe has been used to identify association/dissociation events of protein–ligand bonds. We show that off-rate of molecular dissociation can be estimated by the analysis of the bond lifetime, while the on-rate of molecular association can be estimated by the analysis of the waiting time between two neighboring bond events. However, the analysis relies heavily on subjective judgments and is time-consuming. To automate the process of mapping out bond events from thermal fluctuation data, we develop a hidden Markov model (HMM)-based method. Results: The HMM method represents the bond state by a hidden variable with two values: bound and unbound. The bond association/dissociation is visualized and pinpointed. We apply the method to analyze a key receptor–ligand interaction in the early stage of hemostasis and thrombosis: the von Willebrand factor (VWF) binding to platelet glycoprotein Ibα (GPIbα). The numbers of bond lifetime and waiting time events estimated by the HMM are much more than those estimated by a descriptive statistical method from the same set of raw data. The kinetic parameters estimated by the HMM are in excellent agreement with those by a descriptive statistical analysis, but have much smaller errors for both wild-type and two mutant VWF-A1 domains. Thus, the computerized analysis allows us to speed up the analysis and improve the quality of estimates of receptor–ligand binding kinetics. Contact: jeffwu@isye.gatech.edu or cheng.zhu@bme.gatech.edu PMID:23599504

A quantum chemical study of the structures, stability, and spectroscopy of halogen- and hydrogen-boned complexes between cyanoacetaldehyde and hypochlorous acids

NASA Astrophysics Data System (ADS)

Tang, Qingjie; Guo, Zhenfu; Li, Qingzhong

2014-03-01

The complexes of cyanoacetaldehyde and hypohalous acid (HOX, X = Cl, Br, and I) have been investigated. They can form six different structures (A, B, C, D, E, and F), the former three structures are mainly combined through a N(O)⋯X halogen bond and the latter three structures are maintained mainly by a N(O)⋯H hydrogen bond, although other weaker interactions are also present in most structures. The hydrogen-bonded structures are more stable than the respective halogen-bonded structures. The Osbnd H and Osbnd X bonds in the halogen- and hydrogen-bonded complexes are lengthened and show an observed red shift, while those in the weaker secondary interactions are contracted and display a small blue shift. The orbital interactions in NBO analysis and the electron densities in AIM analysis provide useful and reliable information for the strength of each type of interaction in different structures.

Effect of clearfil protect bond and transbond plus self-etch primer on shear bond strength of orthodontic brackets

PubMed Central

Raji, S. Hamid; Ghorbanipour, Reza; Majdzade, Fateme

2011-01-01

Background: The aim of this study was to evaluate the shear bond strength of an antimicrobial and fluoride-releasing self-etch primer (clearfil protect bond) and compare it with transbond plus self-etch primer and conventional acid etching and priming system. Materials and Methods: Forty-eight extracted human premolars were divided randomly to three groups. In group 1, the teeth were bonded with conventional acid etching and priming method. In group 2, the teeth were bonded with clearfil protect bond self-etch primer, and transbond plus self-etch primer was used to bond the teeth in group 3. The samples were stored in 37°C distilled water and thermocycled. Then, the SBS of the sample was evaluated with Zwick testing machine. Descriptive statistics and the analysis of variances (ANOVA) and Tukey's test and Kruskal-Wallis were used to analyze the data. Results: The results of the ANOVA showed that the mean of group 3 was significantly lower than that of other groups. Most of the sample showed a pattern of failure within the adhesive resin. Conclusion: The shear bond strength of clearfil protect bond and transbond plus self-etch primer was enough for bonding the orthodontic brackets. The mode of failure of bonded brackets with these two self-etch primers is safe for enamel. PMID:23372605

Effect of Cigarette Smoke on Resin Composite Bond Strength to Enamel and Dentin Using Different Adhesive Systems.

PubMed

Theobaldo, J D; Catelan, A; Rodrigues-Filho, U; Marchi, G M; Lima, Danl; Aguiar, Fhb

2016-01-01

To evaluate the microshear bond strength of composite resin restorations in dental blocks with or without exposure to cigarette smoke. Eighty bovine dental blocks were divided into eight groups (n=10) according to the type of adhesive (Scotchbond Multi-Purpose, 3M ESPE, St Paul, MN, USA [SBMP]; Single Bond 2, 3M ESPE [SB]; Clearfil SE Bond, Kuraray Medical Inc, Okayama, Japan [CSEB]; Single Bond Universal, 3M ESPE [SBU]) and exposure to smoke (no exposure; exposure for five days/20 cigarettes per day). The adhesive systems were applied to the tooth structure, and the blocks received a composite restoration made using a matrix of perforated pasta. Data were statistically analyzed using analysis of variance and Tukey test (α<0.05). For enamel, there was no difference between the presence or absence of cigarette smoke (p=0.1397); however, there were differences among the adhesive systems (p<0.001). CSEB showed higher values and did not differ from SBU, but both were statistically different from SB. The SBMP showed intermediate values, while SB demonstrated lower values. For dentin, specimens subjected to cigarette smoke presented bond strength values that were lower when compared with those not exposed to smoke (p<0.001). For the groups without exposure to cigarette smoke, CSEB showed higher values, differing from SBMP. SB and SBU showed intermediary values. For the groups with exposure to cigarette smoke, SBU showed values that were higher and statistically different from SB and CSEB, which presented lower values of bond strength. SBMP demonstrated an intermediate value of bond strength. The exposure of dentin to cigarette smoke influenced the bonding strength of adhesives, but no differences were noted in enamel.

Adhesion of resin composite core materials to dentin.

PubMed

O'Keefe, K L; Powers, J M

2001-01-01

This study determined (1) the effect of polymerization mode of resin composite core materials and dental adhesives on the bond strength to dentin, and (2) if dental adhesives perform as well to dentin etched with phosphoric acid as to dentin etched with self-etching primer. Human third molars were sectioned 2 mm from the highest pulp horn and polished. Three core materials (Fluorocore [dual cured], Core Paste [self-cured], and Clearfil Photo Core [light cured]) and two adhesives (Prime & Bond NT Dual Cure and Clearfil SE Bond [light cured]) were bonded to dentin using two dentin etching conditions. After storage, specimens were debonded in microtension and bond strengths were calculated. Scanning electron micrographs of representative bonding interfaces were analyzed. Analysis showed differences among core materials, adhesives, and etching conditions. Among core materials, dual-cured Fluorocore had the highest bond strengths. There were incompatibilities between self-cured Core Paste and Prime & Bond NT in both etched (0 MPa) and nonetched (3.0 MPa) dentin. Among adhesives, in most cases Clearfil SE Bond had higher bond strengths than Prime & Bond NT and bond strengths were higher to self-etched than to phosphoric acid-etched dentin. Scanning electron micrographs did not show a relationship between resin tags and bond strengths. There were incompatibilities between a self-cured core material and a dual-cured adhesive. All other combinations of core materials and adhesives produced strong in vitro bond strengths both in the self-etched and phosphoric acid-etched conditions.

Relationship between thin-film bond strength as measured by a scratch test, and indentation hardness for bonding agents.

PubMed

Kusakabe, Shusuke; Rawls, H Ralph; Hotta, Masato

2016-03-01

To evaluate thin-film bond strength between a bonding agent and human dentin, using a scratch test, and the characteristics and accuracy of measurement. One-step bonding agents (BeautiBond; Bond Force; Adper Easy Bond; Clearfil tri-S Bond) and two-step bonding agents (Cleafil SE Bond; FL-Bond II) were investigated in this study. Flat dentin surfaces were prepared for extracted human molars. The dentin surfaces were ground and bonding agents were applied and light cured. The thin-film bond strength test of the specimens was evaluated by the critical load at which the coated bonding agent failed and dentin appeared. The scratch mark sections were then observed under a scanning electron microscope. Indentation hardness was evaluated by the variation in depth under an applied load of 10gf. Data were compared by one-way ANOVA with the Scheffé's post hoc multiple comparison test (p<0.05). In addition, thin-film bond strength and indentation hardness were analyzed using analysis of correlation and covariance. The thin-film bond strength of two-step bonding agents were found to be significantly higher than that of one-step bonding agents with small standard deviations. Scratch marks consistently showed adhesive failure in the vicinity of the bonding agent/dentin interface. The indentation hardness showed a trend that two-step bonding agents have greater hardness than one-step bonding agents. A moderately significant correlation (r(2)=0.31) was found between thin-film bond strength and indentation hardness. Thin-film bond strength test is a valid and reliable means of evaluating bond strength in the vicinity of the adhesive interface and is more accurate than other methods currently in use. Further, the thin-film bond strength is influenced by the hardness of the cued bonding agent. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Indirect resin composite restorations bonded to dentin using self-adhesive resin cements applied with an electric current-assisted method.

PubMed

Gotti, Valeria Bisinoto; Feitosa, Victor Pinheiro; Sauro, Salvatore; Correr-Sobrinho, Lourenço; Correr, Americo Bortolazzo

2014-10-01

To evaluate the effects of an electric current-assisted application on the bond strength and interfacial morphology of self-adhesive resin cements bonded to dentin. Indirect resin composite build-ups were luted to prepared dentin surfaces using two self-adhesive resin cements (RelyX Unicem and BisCem) and an ElectroBond device under 0, 20, or 40 μA electrical current. All specimens were submitted to microtensile bond strength test and to interfacial SEM analysis. The electric current-assisted application induced no change (P > 0.05) on the overall bond strength, although RelyX Unicem showed significantly higher bond strength (P < 0.05) than BisCem. Similarly, no differences were observed in terms of interfacial integrity when using the electrical current applicator.

Acoustic Monitoring of Adhesive Bond Curing in Wood Laminates.

NASA Astrophysics Data System (ADS)

Biernacki, Jacek Marek

Challenges in manufacturing of wood products, such as glulam, include difficulty in controlling bonding variables and assessing bond quality. This dissertation investigates an ultrasonic method as a means of monitoring of curing and assessing bond quality in wood laminates. The effect of curing on ultrasonic transmission was studied using specimens of clear Douglas-fir, 100 x 200 x 600 mm, with the adhesive bond in the center of the specimen. Monitoring was performed simultaneously at normal and angular (5 ^circ nominal) incidence to the bond plane. Acoustic measurements were supplemented with destructive cure monitoring, standard bond strength measurement, monitoring of bulk viscosity curing, gel time measurement, and microscopic (SEM) examination. Angular incidence gave greater sensitivity to bond quality and curing status than did normal incidence. Analysis of wave propagation showed that displacement for transmission at a small angle (on the order of 5^circ ) was nearly parallel to the bond, which seems to explain greater sensitivity of angular incidence. Experimental results showed that this method was effective in detection of curing phases, such as spread, penetration, and hardening, defective bonds, and the effect of clamping pressure. An "unloading effect", measured as a relative transmission reduction after the clamping load was released, was sensitive to defective bonds, including uncured (kissing), underspread, and uneven spread bonds. Thick bonds (0.5 and 1.0 mm) caused the greatest increase in transmission, since waves at start of curing were highly attenuated. In angular transmission, thick-bond curing curves showed a characteristic inflection, which may be used to identify thick bonds and measure the curing rate. The results of this dissertation could be utilized to develop commercial systems in glulam manufacturing, which could evaluate: (a) phase of and completion of curing (b) bond quality (c) optimum clamping pressure. Similar systems could also be developed to monitor lumber and panel products curing at high temperature, such as LVL (laminated veneer lumber), OSB (oriented strandboard) and particleboard.

Shear bond strength of orthodontic brackets and disinclusion buttons: effect of water and saliva contamination.

PubMed

Sfondrini, Maria Francesca; Fraticelli, Danilo; Gandini, Paola; Scribante, Andrea

2013-01-01

The aim of this study was to assess the effect of water and saliva contamination on the shear bond strength and failure site of orthodontic brackets and lingual buttons. 120 bovine permanent mandibular incisors were randomly divided into 6 groups of 20 specimens each. Both orthodontic brackets and disinclusion buttons were tested under three different enamel surface conditions: (a) dry, (b) water contamination, and (c) saliva contamination. Brackets and buttons were bonded to the teeth and subsequently tested using a Instron universal testing machine. Shear bond strength values and adhesive failure rate were recorded. Statistical analysis was performed using ANOVA and Tukey tests (strength values) and Chi squared test (ARI Scores). Noncontaminated enamel surfaces showed the highest bond strengths for both brackets and buttons. Under water and saliva contamination orthodontic brackets groups showed significantly lower shear strengths than disinclusion buttons groups. Significant differences in debond locations were found among the groups under the various enamel surface conditions. Water and saliva contamination of enamel during the bonding procedure lowers bond strength values, more with orthodontic brackets than with disinclusion buttons.

Tensile bond strength of filled and unfilled adhesives to dentin.

PubMed

Braga, R R; Cesar, P F; Gonzaga, C C

2000-04-01

To determine the tensile bond strength of three filled and two unfilled adhesives applied to bovine dentin. Fragments of the labial dentin of bovine incisors were embedded in PVC cylinders with self-cure acrylic resin, and ground flat using 200 grit and 600 grit sandpaper. The following adhesive systems were tested (n=10): Prime & Bond NT, Prime & Bond NT dual cure, Prime & Bond 2.1, OptiBond Solo and Single Bond. A 3 mm-diameter bonding surface was delimited using a perforated adhesive tape. After etching with 37% phosphoric acid and adhesive application, a resin-based composite truncated cone (TPH, shade A3) was built. Tensile test was performed after 24 hrs storage in distilled water at 37 degrees C. Failure mode was accessed using a x10 magnification stereomicroscope. Weibull statistical analysis revealed significant differences in the characteristic strength between Single Bond and Prime & Bond NT dual cure, and between Single Bond and Prime & Bond 2.1. The Weibull parameter (m) was statistically similar among the five groups. Single Bond and Prime & Bond NT showed areas of dentin cohesive failure in most of the specimens. For OptiBond Solo, Prime & Bond NT dual cure and Prime & Bond 2.1 failure was predominantly adhesive.

The effect of IDS (immediate dentin sealing) on dentin bond strength under various thermocycling periods

PubMed Central

Leesungbok, Richard; Lee, Sang-Min; Park, Su-Jung; Lee, Suk-Won; Lee, Do Yun; Im, Byung-Jin

2015-01-01

PURPOSE The purpose of this study was to find out the effect of immediate dentin sealing (IDS) on bond strength of ceramic restoration under various thermocycling periods with DBA (dentin bonding agent system). MATERIALS AND METHODS Fifty freshly extracted human mandibular third molars were divided into 5 groups (1 control and 4 experimental groups) of 10 teeth. We removed enamel layer of sound teeth and embedded them which will proceed to be IDS, using All Bond II. A thermocycling was applied to experimental groups for 1, 2, 7, 14 days respectively and was not applied to control group. IPS Empress II for ceramic was acid-etched with ceramic etchant (9.5% HF) and silane was applied. Each ceramic disc was bonded to specimens with Duo-link, dual curable resin cement by means of light curing for 100 seconds. After the cementation procedures, shear bond strength measurement and SEM analysis of the fractured surface were done. The data were analyzed with a one-way ANOVA and Tukey multiple comparison test (α=.05). RESULTS There were no statistically significant differences between 4 experimental groups and control group, however the mean value started to decrease in group 7d, and group 14d showed the lowest mean bond strength in all groups. Also, group 7d and 14d showed distinct exposed dentin and collapsed hybrid layer was observed in SEM analysis. CONCLUSION In the present study, it can be concluded that ceramic restorations like a laminate veneer restoration should be bonded using resin cement within one week after IDS procedure. PMID:26140174

Molecular dynamics analysis of transitions between rotational isomers in polymethylene

NASA Astrophysics Data System (ADS)

Zúñiga, Ignacio; Bahar, Ivet; Dodge, Robert; Mattice, Wayne L.

1991-10-01

Molecular dynamics trajectories have been computed and analyzed for linear chains, with sizes ranging from C10H22 to C100H202, and for cyclic C100H200. All hydrogen atoms are included discretely. All bond lengths, bond angles, and torsion angles are variable. Hazard plots show a tendency, at very short times, for correlations between rotational isomeric transitions at bond i and i±2, in much the same manner as in the Brownian dynamics simulations reported by Helfand and co-workers. This correlation of next nearest neighbor bonds in isolated polyethylene chains is much weaker than the correlation found for next nearest neighbor CH-CH2 bonds in poly(1,4-trans-butadiene) confined to the channel formed by crystalline perhydrotriphenylene [Dodge and Mattice, Macromolecules 24, 2709 (1991)]. Less than half of the rotational isomeric transitions observed in the entire trajectory for C50H102 can be described as strongly coupled next nearest neighbor transitions. If correlated motions are identified with successive transitions, which occur within a time interval of Δt≤1 ps, only 18% of the transitions occur through cooperative motion of bonds i and i±2. An analysis of the entire data set of 2482 rotational isomeric state transitions, observed in a 3.7 ns trajectory for C50H102 at 400 K, was performed using a formalism that treats the transitions at different bonds as being independent. On time scales of 0.1 ns or longer, the analysis based on independent bonds accounts reasonably well for the results from the molecular dynamics simulations. At shorter times the molecular dynamics simulation reveals a higher mobility than implied by the analysis assuming independent bonds, presumably due to the influence of correlations that are important at shorter times.

Strength order and nature of the π-hole bond of cyanuric chloride and 1,3,5-triazine with halide.

PubMed

Wang, Hui; Li, Chen; Wang, Weizhou; Jin, Wei Jun

2015-08-28

The (13)C NMR chemical shift moving upfield indicates the main model of π-holeX(-) bond between cyanuric chloride/1,3,5-triazine (3ClN/3N), which possess both the π-hole and σ-hole, and X(-). (13)C NMR and UV absorption titration in acetonitrile confirmed that the bonding abilities of 3ClN/3N with X(-) follow the order I(-) > Br(-) > Cl(-), which is apparently the order of the charge transfer ability of halide to 3ClN/3N. Chemical calculations showed that the bonding abilities in solution were essentially consistent with those obtained by titration experiments. However, the results in the gas phase were the reverse, i.e., π-holeCl(-) > π-holeBr(-) > π-holeI(-) in bonding energy, which obeys the order of electrostatic interaction. In fact, the π-hole bond and σ-hole bond compete with solvation and possible anion-hydrogen bond between a solvent molecule and a halide in solution. An explanation is that the apparent charge transfer order of π-/σ-holeI(-) > π-/σ-holeBr(-) > π-/σ-holeCl(-) occurs for weak π-hole bonds and σ-hole bonds, whereas the order of electrostatic attraction of π-/σ-holeCl(-) > π-/σ-holeBr(-) > π-/σ-holeI(-) is valid for strong bonds. It can be concluded by combining energy decomposition analysis and natural bond orbital analysis that the π-holeX(-) bond and σ-holeX(-) bond are electrostatically attractive in nature regardless of whether the order is I(-) > Br(-) > Cl(-) or the reverse.

Ionic Liquids as a Basis Context for Developing High school Chemistry Teaching Materials

NASA Astrophysics Data System (ADS)

Hernani; Mudzakir, A.; Sumarna, O.

2017-02-01

This research aims to produce a map of connectedness highschool chemical content with the context of the modern chemical materials applications based on ionic liquids. The research method is content analysis of journal articles related to the ionic liquid materials and the textbooks of high school chemistry and textbooks of general chemistry at the university. The instrument used is the development format of basic text that connect and combine content and context. The results showed the connectedness between: (1) the context lubricants ionic liquid with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, the elements of main group, the elements of transition group, and the classification of macromolecules; (2) the context of fuel cell electrolite with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, Volta cell, and electrolysis cell; (3) the contect of nanocellulose with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, colloid, carbon compound, and the classification of macromolecules; and (4) the context of artificial muscle system with the content of ionic bond, covalent bond, metal bonding, interaction between the particles of matter, hydrocarbons, electrolytes and non-electrolytes, and the classification of macromolecules. Based on the result of this content analysis, the context of ionic liquid is predicted can be utilized for the enrichment of high school chemistry and has the potential to become teaching material’s context of high school chemistry in the future.

Evans hole and non linear optical activity in Bis(melaminium) sulphate dihydrate: A vibrational spectral study.

PubMed

Suresh Kumar, V R; Binoy, J; Dawn Dharma Roy, S; Marchewka, M K; Jayakumar, V S

2015-01-01

Bis(melaminium) sulphate dihydrate (BMSD), an interesting melaminium derivative for nonlinear optical activity, has been subjected to vibrational spectral analysis using FT IR and FT Raman spectra. The analysis has been aided by the Potential Energy Distribution (PED) of vibrational spectral bands, derived using density functional theory (DFT) at B3LYP/6-31G(d) level. The geometry is found to correlate well with the XRD structure and the band profiles for certain vibrations in the finger print region have been theoretically explained using Evans hole. The detailed Natural Bond Orbital (NBO) analysis of the hydrogen bonding in BMSD has also been carried out to understand the correlation between the stabilization energy of hyperconjugation of the lone pair of donor with the σ(∗) orbital of hydrogen-acceptor bond and the strength of hydrogen bond. The theoretical calculation shows that BMSD has NLO efficiency, 2.66 times that of urea. The frontier molecular orbital analysis points to a charge transfer, which contributes to NLO activity, through N-H…O intermolecular hydrogen bonding between the melaminium ring and the sulphate. The molecular electrostatic potential (MEP) mapping has also been performed for the detailed analysis of the mutual interactions between melaminium ring and sulphate ion. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydrogen bonded C-H···Y (Y = O, S, Hal) molecular complexes: A natural bond orbital analysis

NASA Astrophysics Data System (ADS)

Isaev, A. N.

2016-03-01

Hydrogen bonded C-H···Y complexes formed by H2O, H2S molecules, hydrogen halides, and halogen-ions with methane, halogen substituted methane as well as with the C2H2 and NCH molecules were studied at the MP2/aug-cc-pVDZ level. The structure of NBOs corresponding to lone pair of acceptor Y, n Y, and vacant anti-σ-bond C-H of proton donor was analyzed and estimates of second order perturbation energy E(2) characterizing donor-acceptor n Y → σ C-H * charge-transfer interaction were obtained. Computational results for complexes of methane and its halogen substituted derivatives show that for each set of analogous structures, the EnY→σ*C-H (2) energy tends to grow with an increase in the s-component percentage in the lone pair NBO of acceptor Y. Calculations for different C···Y distances show that the equilibrium geometries of complexes lie in the region where the E(2) energy is highest and it changes symbatically with the length of the covalent E-H bond when the R(C···Y) distance is varied. The performed analysis allows us to divide the hydrogen bonded complexes into two groups, depending on the pattern of overlapping for NBOs of the hydrogen bridge.

Comovements in government bond markets: A minimum spanning tree analysis

NASA Astrophysics Data System (ADS)

Gilmore, Claire G.; Lucey, Brian M.; Boscia, Marian W.

2010-11-01

The concept of a minimum spanning tree (MST) is used to study patterns of comovements for a set of twenty government bond market indices for developed North American, European, and Asian countries. We show how the MST and its related hierarchical tree evolve over time and describe the dynamic development of market linkages. Over the sample period, 1993-2008, linkages between markets have decreased somewhat. However, a subset of European Union (EU) bond markets does show increasing levels of comovements. The evolution of distinct groups within the Eurozone is also examined. The implications of our findings for portfolio diversification benefits are outlined.

Chemical bonds and vibrational properties of ordered (U, Np, Pu) mixed oxides

NASA Astrophysics Data System (ADS)

Yang, Yu; Zhang, Ping

2013-01-01

We use density functional theory +U to investigate the chemical bonding characters and vibrational properties of the ordered (U, Np, Pu) mixed oxides (MOXs), UNpO4,NpPuO4, and UPuO4. It is found that the 5f electronic states of different actinide elements keep their localized characters in all three MOXs. The occupied 5f electronic states of different actinide elements do not overlap with each other and tend to distribute over the energy band gap of the other actinide element's 5f states. As a result, the three ordered MOXs all show smaller band gaps than those of the component dioxides, with values of 0.91, 1.47, and 0.19 eV for UNpO4,NpPuO4, and UPuO4, respectively. Through careful charge density analysis, we further show that the U-O and Pu-O bonds in MOXs show more ionic character than in UO2 and PuO2, while the Np-O bonds show more covalent character than in NpO2. The change in covalencies in the chemical bonds leads to vibrational frequencies of oxygen atoms that are different in MOXs.

A theoretical study on the characteristics of the intermolecular interactions in the active site of human androsterone sulphotransferase: DFT calculations of NQR and NMR parameters and QTAIM analysis.

PubMed

Astani, Elahe K; Heshmati, Emran; Chen, Chun-Jung; Hadipour, Nasser L

2016-07-01

A theoretical study at the level of density functional theory (DFT) was performed to characterize noncovalent intermolecular interactions, especially hydrogen bond interactions, in the active site of enzyme human androsterone sulphotransferase (SULT2A1/ADT). Geometry optimization, interaction energy, (2)H, (14)N, and (17)O electric field gradient (EFG) tensors, (1)H, (13)C, (17)O, and (15)N chemical shielding (CS) tensors, Natural Bonding Orbital (NBO) analysis, and quantum theory of atoms in molecules (QTAIM) analysis of this active site were investigated. It was found that androsterone (ADT) is able to form hydrogen bonds with residues Ser80, Ile82, and His99 of the active site. The interaction energy calculations and NBO analysis revealed that the ADT molecule forms the strongest hydrogen bond with Ser80. Results revealed that ADT interacts with the other residues through electrostatic and Van der Waals interactions. Results showed that these hydrogen bonds influence on the calculated (2)H, (14)N, and (17)O quadrupole coupling constants (QCCs), as well as (1)H, (13)C, (17)O, and (15)N CS tensors. The magnitude of the QCC and CS changes at each nucleus depends directly on its amount of contribution to the hydrogen bond interaction. Copyright © 2016 Elsevier Inc. All rights reserved.

New Insights into the Folding of a β-Sheet Miniprotein in a Reduced Space of Collective Hydrogen Bond Variables: Application to a Hydrodynamic Analysis of the Folding Flow

PubMed Central

Kalgin, Igor V.; Caflisch, Amedeo; Chekmarev, Sergei F.; Karplus, Martin

2013-01-01

A new analysis of the 20 μs equilibrium folding/unfolding molecular dynamics simulations of the three-stranded antiparallel β-sheet miniprotein (beta3s) in implicit solvent is presented. The conformation space is reduced in dimensionality by introduction of linear combinations of hydrogen bond distances as the collective variables making use of a specially adapted Principal Component Analysis (PCA); i.e., to make structured conformations more pronounced, only the formed bonds are included in determining the principal components. It is shown that a three-dimensional (3D) subspace gives a meaningful representation of the folding behavior. The first component, to which eight native hydrogen bonds make the major contribution (four in each beta hairpin), is found to play the role of the reaction coordinate for the overall folding process, while the second and third components distinguish the structured conformations. The representative points of the trajectory in the 3D space are grouped into conformational clusters that correspond to locally stable conformations of beta3s identified in earlier work. A simplified kinetic network based on the three components is constructed and it is complemented by a hydrodynamic analysis. The latter, making use of “passive tracers” in 3D space, indicates that the folding flow is much more complex than suggested by the kinetic network. A 2D representation of streamlines shows there are vortices which correspond to repeated local rearrangement, not only around minima of the free energy surface, but also in flat regions between minima. The vortices revealed by the hydrodynamic analysis are apparently not evident in folding pathways generated by transition-path sampling. Making use of the fact that the values of the collective hydrogen bond variables are linearly related to the Cartesian coordinate space, the RMSD between clusters is determined. Interestingly, the transition rates show an approximate exponential correlation with distance in the hydrogen bond subspace. Comparison with the many published studies shows good agreement with the present analysis for the parts that can be compared, supporting the robust character of our understanding of this “hydrogen atom” of protein folding. PMID:23621790

Fibre-Reinforced Adhesive for Structure Anchoring

NASA Astrophysics Data System (ADS)

Barnat, J.; Bajer, M.

2015-11-01

The topic of this paper is the glue-concrete interface of bonded anchors loaded by tension force. The paper is closely focused on bond strength experiments using high strength concrete up to class C50/60 or higher together with pure epoxy resin and fibre-reinforced resin. The goal of this research is to find the limits of the effective use of such glue types in high performance concrete, and also to verify the most commonly used design methods for bonded anchors. The presented research includes experimental analysis of the glue-concrete interface and the influence of its parameters on anchor behaviour. The presented analysis shows some problems of the 'separated failure modes' approach and also presents experimentally verified bond strength values obtained for the currently most widespread glue types. Results of fibre reinforced epoxy resin are also presented in this paper.

Comprehensive DFT study on molecular structures of Lewisites in support of the Chemical Weapons Convention

NASA Astrophysics Data System (ADS)

Saeidian, Hamid; Sahandi, Morteza

2015-11-01

The structure of all of Lewisite's stereoisomers has been examined by B3LYP/6-311++G(3df,3pd) calculations. The geometry analysis for trans Lewisite L1-1 shows that the calculated bond angles, bond distances and dipole moment have a satisfactory relation compared with experimental values. HOMO-LUMO analysis of Lewisites reveals that L1-2 and L3-7 have the maximum and minimum electrophilicity index, respectively. The calculated chemical shifts were compared with experimental data, showing a very good agreement both for 1H and 13C. The vibrational and Raman frequencies of Lewisites have been precisely assigned and theoretical data were compared with the experimental vibrations. The bonding trends and Mulliken and atomic polar tensor charge distribution in Lewisites can be explained by the Bent's rule and the donor-acceptor interaction, respectively.

Study of vibrational spectra and hydrogen bonding network in dimeric and tetrameric model of ampicillin using DFT and AIM approach

NASA Astrophysics Data System (ADS)

Shukla, Anuradha; Khan, Eram; Tandon, Poonam; Sinha, Kirti

2017-03-01

Ampicillin is a β-lactam antibiotic that is active against both gram-positive and gram-negative bacteria and is widely used for the treatment of infections. In this work, molecular properties of ampicillin are calculated on the basis of calculations on its dimeric and tetrameric models using DFT/B3LYP/6-311G(d,p). HOMO-LUMO energy gap shows that chemical reactivity of tetrameric model of ampicillin is higher than the dimeric and monomeric model of ampicillin. To get a better understanding of intra and intermolecular bonding and interactions among bonds, NBO analysis is carried out with tetrameric model of ampicillin, and is further finalized with an 'quantum theory of atoms-in-molecules' (QTAIM) analysis. The binding energy of dimeric model of ampicillin is calculated as -26.84 kcal/mol and -29.34 kcal/mol using AIM and DFT calculations respectively. The global electrophilicity index (ω = 2.8118 eV) of tetrameric model of ampicillin shows that this behaves as a strong electrophile in comparison to dimeric and monomeric model of ampicillin. The FT-Raman and FT-IR spectra were recorded in the solid phase, and interpreted in terms of potential energy distribution analysis. A collective theoretical and experimental vibrational analysis approves the presence of hydrogen bonds in the ampicillin molecule.

Accounting for the differences in the structures and relative energies of the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I4 2+, the Se-I pi-bonded Se2I4 2+, and their higher-energy isomers by AIM, MO, NBO, and VB methodologies.

PubMed

Brownridge, Scott; Crawford, Margaret-Jane; Du, Hongbin; Harcourt, Richard D; Knapp, Carsten; Laitinen, Risto S; Passmore, Jack; Rautiainen, J Mikko; Suontamo, Reijo J; Valkonen, Jussi

2007-02-05

The bonding in the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I42+ (three sigma + two pi bonds), the Se-I pi-bonded Se2I42+ (four sigma + one pi bonds), and their higher-energy isomers have been studied using modern DFT and ab initio calculations and theoretical analysis methods: atoms in molecules (AIM), molecular orbital (MO), natural bond orbital (NBO), and valence bond (VB) analyses, giving their relative energies, theoretical bond orders, and atomic charges. The aim of this work was to seek theory-based answers to four main questions: (1) Are the previously proposed simple pi*-pi* bonding models valid for S2I42+ and Se2I42+? (2) What accounts for the difference in the structures of S2I42+ and Se2I42+? (3) Why are the classically bonded isolobal P2I4 and As2I4 structures not adopted? (4) Is the high experimentally observed S-S bond order supported by theoretical bond orders, and how does it relate to high bond orders between other heavier main group elements? The AIM analysis confirmed the high bond orders and established that the weak bonds observed in S2I42+ and Se2I42+ are real and the bonding in these cations is covalent in nature. The full MO analysis confirmed that S2I42+ contains three sigma and two pi bonds, that the positive charge is essentially equally distributed over all atoms, that the bonding between S2 and two I2+ units in S2I42+ is best described by two mutually perpendicular 4c2e pi*-pi* bonds, and that in Se2I42+, two SeI2+ moieties are joined by a 6c2e pi*-pi* bond, both in agreement with previously suggested models. The VB treatment provided a complementary approach to MO analysis and provided insight how the formation of the weak bonds affects the other bonds. The NBO analysis and the calculated AIM charges showed that the minimization of the electrostatic repulsion between EI2+ units (E = S, Se) and the delocalization of the positive charge are the main factors that explain why the nonclassical structures are favored for S2I42+ and Se2I42+. The difference in the structures of S2I42+ and Se2I42+ is related to the high strength of the S-S pi bond compared to the weak S-I sigma bond and the additional stabilization from increased delocalization of positive charge in the structure of S2I42+ compared to the structure of Se2I42+. The investigation of the E2X42+ series (E = S, Se, Te; X = Cl, Br, I) revealed that only S2I42+ adopts the highly np pi-np pi (n > or = 3)-bonded structure, while all other dications favor the pi-bonded Se2I42+ structure. Theoretical bond order calculations for S2I42+ confirm the previously presented experimentally based bond orders for S-S (2.1-2.3) and I-I (1.3-1.5) bonds. The S-S bond is determined to have the highest reported S-S bond order in an isolated compound and has a bond order that is either similar to or slightly less than the Si-Si bond order in the proposed triply bonded [(Me3Si)2CH]2(iPr)SiSi triple bond SiSi(iPr)[CH(SiMe3)2]2 depending on the definition of bond orders used.

Bond strength of universal adhesives: A systematic review and meta-analysis.

PubMed

Rosa, Wellington Luiz de Oliveira da; Piva, Evandro; Silva, Adriana Fernandes da

2015-07-01

A systematic review was conducted to determine whether the etch-and-rinse or self-etching mode is the best protocol for dentin and enamel adhesion by universal adhesives. This report followed the PRISMA Statement. A total of 10 articles were included in the meta-analysis. Two reviewers performed a literature search up to October 2014 in eight databases: PubMed, Web of Science, Scopus, BBO, SciELO, LILACS, IBECS and The Cochrane Library. In vitro studies evaluating the bond strength of universal adhesives to dentin and/or enamel by the etch-and-rinse and self-etch strategies were eligible to be selected. Statistical analyses were conducted using RevMan 5.1 (The Cochrane Collaboration, Copenhagen, Denmark). A global comparison was performed with random-effects models at a significance level of p<0.05. The analysis of dentin micro-tensile bond strength showed no statistically significant difference between the etch-and-rinse and self-etch strategies for mild universal adhesives (p≥0.05). However, for the ultra-mild All-Bond Universal adhesive, the etch-and-rinse strategy was significantly different than the self-etch mode in terms of dentin micro-tensile bond strength, as well as in the global analysis of enamel micro-tensile and micro-shear bond strength (p≤0.05). The enamel bond strength of universal adhesives is improved with prior phosphoric acid etching. However, this effect was not evident for dentin with the use of mild universal adhesives with the etch-and-rinse strategy. Selective enamel etching prior to the application of a mild universal adhesive is an advisable strategy for optimizing bonding. Copyright © 2015 Elsevier Ltd. All rights reserved.

Compositional analysis of dilute nitride doped indium antimonide bulk crystal by VDS technique

NASA Astrophysics Data System (ADS)

Deshpande, Manisha; Maske, Dilip; Choudhari, Rashmi; Arora, Brij Mohan; Gadkari, Dattatray

2016-05-01

Dilute nitrides are suitable materials for fabrication of devices in detection of long wavelength infrared region. Dilute nitride doped Indium antimonide bulk crystals were grown using vertical directional solidification technique. The compositional characteristics of the crystals were carried out using EDS. The analysis was simulated and compared with observations using DTSA II software for accuracy. The ingots have uniform composition of Indium and Antimony. The actual nitrogen composition measured using EDS was 0.136% for doped nitrogen composition 0.1% except near conical end where it was 0.1%. The study of bonding between nitrogen, Indium and antimony was carried out using SIMS. The analysis shows strong presence of In-N bonding along with In-Sb bonds which indicates nitrogen has replaced antimony atoms in crystal lattice.

Shear Bond Strength of Orthodontic Brackets and Disinclusion Buttons: Effect of Water and Saliva Contamination

PubMed Central

Sfondrini, Maria Francesca; Fraticelli, Danilo; Gandini, Paola

2013-01-01

Purpose. The aim of this study was to assess the effect of water and saliva contamination on the shear bond strength and failure site of orthodontic brackets and lingual buttons. Materials and Methods. 120 bovine permanent mandibular incisors were randomly divided into 6 groups of 20 specimens each. Both orthodontic brackets and disinclusion buttons were tested under three different enamel surface conditions: (a) dry, (b) water contamination, and (c) saliva contamination. Brackets and buttons were bonded to the teeth and subsequently tested using a Instron universal testing machine. Shear bond strength values and adhesive failure rate were recorded. Statistical analysis was performed using ANOVA and Tukey tests (strength values) and Chi squared test (ARI Scores). Results. Noncontaminated enamel surfaces showed the highest bond strengths for both brackets and buttons. Under water and saliva contamination orthodontic brackets groups showed significantly lower shear strengths than disinclusion buttons groups. Significant differences in debond locations were found among the groups under the various enamel surface conditions. Conclusions. Water and saliva contamination of enamel during the bonding procedure lowers bond strength values, more with orthodontic brackets than with disinclusion buttons. PMID:23762825

Effect of Dentin Wetness on the Bond Strength of Universal Adhesives.

PubMed

Choi, An-Na; Lee, Ji-Hye; Son, Sung-Ae; Jung, Kyoung-Hwa; Kwon, Yong Hoon; Park, Jeong-Kil

2017-10-25

The effects of dentin wetness on the bond strength and adhesive interface morphology of universal adhesives have been investigated using micro-tensile bond strength (μTBS) testing and confocal laser scanning microscopy (CLSM). Seventy-two human third molars were wet ground to expose flat dentin surfaces. They were divided into three groups according to the air-drying time of the dentin surfaces: 0 (without air drying), 5, and 10 s. The dentin surfaces were then treated with three universal adhesives: G-Premio Bond, Single Bond Universal, and All-Bond Universal in self-etch or etch-and-rinse mode. After composite build up, a μTBS test was performed. One additional tooth was prepared for each group by staining the adhesives with 0.01 wt % of Rhodamine B fluorescent dye for CLSM analysis. The data were analyzed statistically using ANOVA and Tukey's post hoc tests (α = 0.05). Two-way ANOVA showed significant differences among the adhesive systems and dentin moisture conditions. An interaction effect was also observed ( p < 0.05). One-way ANOVA showed that All-Bond Universal was the only material influenced by the wetness of the dentin surfaces. Wetness of the dentin surface is a factor influencing the micro-tensile bond strength of universal adhesives.

Effect of Dentin Wetness on the Bond Strength of Universal Adhesives

PubMed Central

Lee, Ji-Hye; Son, Sung-Ae; Jung, Kyoung-Hwa; Kwon, Yong Hoon

2017-01-01

The effects of dentin wetness on the bond strength and adhesive interface morphology of universal adhesives have been investigated using micro-tensile bond strength (μTBS) testing and confocal laser scanning microscopy (CLSM). Seventy-two human third molars were wet ground to expose flat dentin surfaces. They were divided into three groups according to the air-drying time of the dentin surfaces: 0 (without air drying), 5, and 10 s. The dentin surfaces were then treated with three universal adhesives: G-Premio Bond, Single Bond Universal, and All-Bond Universal in self-etch or etch-and-rinse mode. After composite build up, a μTBS test was performed. One additional tooth was prepared for each group by staining the adhesives with 0.01 wt % of Rhodamine B fluorescent dye for CLSM analysis. The data were analyzed statistically using ANOVA and Tukey’s post hoc tests (α = 0.05). Two-way ANOVA showed significant differences among the adhesive systems and dentin moisture conditions. An interaction effect was also observed (p < 0.05). One-way ANOVA showed that All-Bond Universal was the only material influenced by the wetness of the dentin surfaces. Wetness of the dentin surface is a factor influencing the micro-tensile bond strength of universal adhesives. PMID:29068404

Microtensile bond strength of composite resin to human enamel prepared using erbium: Yttrium aluminum garnet laser.

PubMed

Delfino, Carina Sinclér; Souza-Zaroni, Wanessa Christine; Corona, Silmara Aparecida Milori; Palma-Dibb, Regina Guenka

2007-02-01

The Erbium: Yttrium Aluminum Garnet (YAG) laser used for preparation of cavity can alter the substrate and it could influence the bond strength of enamel. The aim of this in vitro study was to evaluate the influence of Er:YAG laser's energy using microtensile bond test. Three groups were obtained (cavity preparation) and each group was divided into two subgroups (adhesive system). After that the adhesive protocol was performed, sections with a cross-sectional area of 0.8 mm2 (+/-0.2 mm2) were obtained. The specimens were mounted in a universal testing machine (0.5 mm/min). Statistical analysis showed a decrease in bond strength for lased groups (p < 0.01) and when the total-etching adhesive system was used the laser 300 mJ subgroup showed higher bond strength compared to the laser 250 mJ (p < 0.01). It was concluded that the cavities prepared using laser appear less receptive to adhesive procedures than conventional bur-cut cavities. Copyright 2006 Wiley Periodicals, Inc.

Can You Party Your Way to Better Health? A Propensity Score Analysis of Block Parties and Health

PubMed Central

Dean, Lorraine T.; Hillier, Amy; Chau-Glendinning, Hang; Subramanian, SV; Williams, David R.; Kawachi, Ichiro

2015-01-01

While other indicators of social capital have been linked to health, the role of block parties on health in Black neighborhoods and on Black residents is understudied. Block parties exhibit several features of bonding social capital and are present in nearly 90% of Philadelphia’s predominantly Black neighborhoods. This analysis investigated: (1) whether or not block parties are an indicator of bonding social capital in Black neighborhoods; (2) the degree to which block parties might be related to self-rated health in the ways that other bonding social indicators are related to health; and (3) whether or not block parties are associated with average self-rated health for Black residents particularly. Using census tract-level indicators of bonding social capital and records of block parties from 2003 to 2008 for 381 Philadelphia neighborhoods (defined by census tracts), an ecological-level propensity score was generated to assess the propensity for a block party, adjusting for population demographics, neighborhood characteristics, neighborhood resources and violent crime. Results indicate that in multivariable regression, block parties were associated with increased bonding social capital in Black neighborhoods; however, the calculation of the average effect of the treatment on the treated (ATT) within each propensity score strata showed no effect of block parties on average self-rated health for Black residents. Block parties may be an indicator of bonding social capital in Philadelphia’s predominantly Black neighborhoods, but this analysis did not show a direct association between block parties and self-rated health for Black residents. Further research should consider what other health outcomes or behaviors block parties may be related to and how interventionists can leverage block parties for health promotion. PMID:26117555

A new polymer nanocomposite repair material for restoring wellbore seal integrity

DOE PAGES

Genedy, Moneeb; Kandil, Usama F.; Matteo, Edward N.; ...

2017-03-01

Seal integrity of functional oil wells and abandoned wellbores used for CO 2 subsequent storage has become of significant interest with the oil and gas leaks worldwide. This is attributed to the fact that wellbores intersecting geographical formations contain potential leakage pathways. One of the critical leakage pathways is the cement-shale interface. In this study, we examine the efficiency of a new polymer nanocomposite repair material that can be injected for sealing micro annulus in wellbores. The bond strength and microstructure of the interface of Type G oil well cement (reference), microfine cement, Novolac epoxy incorporating Neat, 0.25%, 0.5%, andmore » 1.0% Aluminum Nanoparticles (ANPs) with shale is investigated. Interfacial bond strength testing shows that injected microfine cement repair has considerably low bond strength, while ANPs-epoxy nanocomposites have a bond strength that is an order of magnitude higher than cement. Microscopic investigations of the interface show that micro annulus interfacial cracks with widths up to 40 μm were observed at the cement-shale interface while these cracks were absent at the cement-epoxy-shale interface. Finally, Fourier Transform Infrared and Dynamic mechanical analysis measurements showed that ANPs improve interfacial bond by limiting epoxy crosslinking, and therefore allowing epoxy to form robust bonds with cement and shale.« less

GROUT-CONCRETE INTERFACE BOND PERFORMANCE: EFFECT OF INTERFACE MOISTURE ON THE TENSILE BOND STRENGTH AND GROUT MICROSTRUCTURE.

PubMed

De la Varga, I; Muñoz, J F; Bentz, D P; Spragg, R P; Stutzman, P E; Graybeal, B A

2018-05-01

Bond between two cementitious materials is crucial in applications such as repairs, overlays, and connections of prefabricated bridge elements (PBEs), to name just a few. It is the latter that has special interest to the authors of this paper. After performing a dimensional stability study on grout-like materials commonly used as connections between PBEs, it was observed that the so-called 'non-shrink' cementitious grouts showed a considerable amount of early-age shrinkage. This might have negative effects on the integrity of the structure, due not only to the grout material's early degradation, but also to a possible loss of bond between the grout and the prefabricated concrete element. Many factors affect the bond strength between two cementitious materials (e.g., grout-concrete), the presence of moisture at the existing concrete substrate surface being one of them. In this regard, pre-moistening the concrete substrate surface prior to the application of the grout material is sometimes recommended for bond enhancement. This topic has been the focus of numerous research studies in the past; however, there is still controversy among practitioners on the real benefits that this practice might provide. This paper evaluates the tensile bond performance of two non-shrink cementitious grouts applied to the exposed aggregate surface of a concrete substrate, and how the supply of moisture at the grout-concrete interface affects the bond strength. "Pull-off" bond results show increased tensile bond strength when the concrete surface is pre-moistened. Reasons to explain the observed increased bond strength are given after a careful microstructural analysis of the grout-concrete interface. Interfaces where sufficient moisture is provided to the concrete substrate such that moisture movement from the grout is prevented show reduced porosity and increased hydration on the grout side of the interface, which is thought to directly contribute to the increased tensile bond strength.

Experimetal study on the FRP-concrete bond behavior under repeated loadings

NASA Astrophysics Data System (ADS)

Lee, J.-Y.; Yi, C.-K.; Cheong, Y.-G.

2009-11-01

In this study, the effects of repeated loads on the FRP-concrete bond strength were investigated experimentally by direct pull out tests according to CSA S806-02. A conventional reinforcing steel bar and two types of glass-fiber-reinforced plastic (GFRP) bars were embedded in concrete and tested under four different loading patterns. The bond strength-slip curves of the bars were obtained and analyzed. The results showed that the maximum bond strengths under the repeated loads differed from those obtained under monotonic ones. In addition, noticeable differences in degradation of the bond strength with respect to the magnitude of slip were observed between the different bar types tested. On the basis of an image analysis of failure surfaces, they were attributed to the different bond failure mechanisms associated with the steel and GFRP bars.

Continuous feelings of love? The parental bond from pregnancy to toddlerhood.

PubMed

de Cock, Evi S A; Henrichs, Jens; Vreeswijk, Charlotte M J M; Maas, A Janneke B M; Rijk, Catharina H A M; van Bakel, Hedwig J A

2016-02-01

Both prenatal and postnatal parental bonding (i.e., the affective tie from parent to child) have important effects on parental and child functioning. However, research on the continuity and correlates of parental bonding is lacking. Therefore, the goal of the present study was to examine the stability of bonding levels and to explore distinct bonding patterns with a latent class analysis. Moreover, the correlates of these bonding patterns in the parental-, child-, and contextual domain were studied. Levels of maternal (N = 370) and paternal (N = 292) bonding and potential correlates were assessed at 26 weeks of pregnancy, 6 months, and 24 months postpartum. Results showed moderate stability of bonding from pregnancy to toddlerhood. For both mothers and fathers, 4 distinct bonding patterns were found. Parents with low bonding patterns were characterized by increased anxiety and parenting stress, less partner support, less adaptive personality profiles, and children with difficult temperament. These findings indicate the importance of monitoring young children's parents with poor levels of bonding as their bonding patterns remain stable from pregnancy until toddlerhood and because those parents experience problems in multiple domains. (c) 2016 APA, all rights reserved).

On the interpretation of domain averaged Fermi hole analyses of correlated wavefunctions.

PubMed

Francisco, E; Martín Pendás, A; Costales, Aurora

2014-03-14

Few methods allow for a physically sound analysis of chemical bonds in cases where electron correlation may be a relevant factor. The domain averaged Fermi hole (DAFH) analysis, a tool firstly proposed by Robert Ponec in the 1990's to provide interpretations of the chemical bonding existing between two fragments Ω and Ω' that divide the real space exhaustively, is one of them. This method allows for a partition of the delocalization index or bond order between Ω and Ω' into one electron contributions, but the chemical interpretation of its parameters has been firmly established only for single determinant wavefunctions. In this paper we report a general interpretation based on the concept of excluded density that is also valid for correlated descriptions. Both analytical models and actual computations on a set of simple molecules (H2, N2, LiH, and CO) are discussed, and a classification of the possible DAFH situations is presented. Our results show that this kind of analysis may reveal several correlated assisted bonding patterns that might be difficult to detect using other methods. In agreement with previous knowledge, we find that the effective bond order in covalent links decreases due to localization of electrons driven by Coulomb correlation.

Examining water in model membranes by near infrared spectroscopy and multivariate analysis.

PubMed

Wenz, Jorge J

2018-03-01

By exploiting the sensitivity of the NIR spectrum, particularly the first overtone of water, to the number and strength of hydrogen bonds, the hydrogen bond network and water polymerization in membranes of DMPA (1,2-dimyristoyl-sn-glycero-3-phosphate) and DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) was investigated as a function of the temperature and the presence of this two phospholipids having the same tail but different polar head. Principal components analysis performed on the spectra was used to disclose subtle spectral changes that mirror the alteration of the vibrational energy of the water O-H bonds, as a measure of the H-bond network. Temperature showed a dominating effect on the H-bond network. Increasing temperatures diminished the number of strongly H-bonded water molecules and increased the number of weakly H-bonded waters. This main effect of temperature was missing after the subtraction of the pure water spectra from the lipid-containing ones. An intriguing secondary effect of temperature was also revealed. Phospholipids exhibited an effect qualitatively similar to that of the temperature. DMPA, and particularly DMPC, disrupted the H-bond network in the neighboring lipid-water interface, reducing water polymerization and strengthening the water O-H bonds. The type of the polar head affects the H-bonds more than duplicate the concentration of the lipid. A connection between head group structure and the effect on the H-bonds network, and the existence of two populations of water molecules are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Comprehensive analysis of individual pulp fiber bonds quantifies the mechanisms of fiber bonding in paper

PubMed Central

Hirn, Ulrich; Schennach, Robert

2015-01-01

The process of papermaking requires substantial amounts of energy and wood consumption, which contributes to larger environmental costs. In order to optimize the production of papermaking to suit its many applications in material science and engineering, a quantitative understanding of bonding forces between the individual pulp fibers is of importance. Here we show the first approach to quantify the bonding energies contributed by the individual bonding mechanisms. We calculated the impact of the following mechanisms necessary for paper formation: mechanical interlocking, interdiffusion, capillary bridges, hydrogen bonding, Van der Waals forces, and Coulomb forces on the bonding energy. Experimental results quantify the area in molecular contact necessary for bonding. Atomic force microscopy experiments derive the impact of mechanical interlocking. Capillary bridges also contribute to the bond. A model based on the crystal structure of cellulose leads to values for the chemical bonds. In contrast to general believe which favors hydrogen bonding Van der Waals bonds play the most important role according to our model. Comparison with experimentally derived bond energies support the presented model. This study characterizes bond formation between pulp fibers leading to insight that could be potentially used to optimize the papermaking process, while reducing energy and wood consumption. PMID:26000898

Compositional analysis of dilute nitride doped indium antimonide bulk crystal by VDS technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deshpande, Manisha, E-mail: manishauj@gmail.com; Department of Physics, Mithibai College, Vile Parle; Maske, Dilip

2016-05-06

Dilute nitrides are suitable materials for fabrication of devices in detection of long wavelength infrared region. Dilute nitride doped Indium antimonide bulk crystals were grown using vertical directional solidification technique. The compositional characteristics of the crystals were carried out using EDS. The analysis was simulated and compared with observations using DTSA II software for accuracy. The ingots have uniform composition of Indium and Antimony. The actual nitrogen composition measured using EDS was 0.136% for doped nitrogen composition 0.1% except near conical end where it was 0.1%. The study of bonding between nitrogen, Indium and antimony was carried out using SIMS.more » The analysis shows strong presence of In-N bonding along with In-Sb bonds which indicates nitrogen has replaced antimony atoms in crystal lattice.« less

Synthesis, structural, DFT studies, docking and antibacterial activity of a xanthene based hydrazone ligand

NASA Astrophysics Data System (ADS)

Naseem, Saira; Khalid, Muhammad; Tahir, Muhammad Nawaz; Halim, Mohammad A.; Braga, Ataualpa A. C.; Naseer, Muhammad Moazzam; Shafiq, Zahid

2017-09-01

Herein, we present the synthesis of novel xanthene-based hydrazone (1). The chemical structure of 1 was resolved using spectroscopic techniques such as NMR, FT-IR, UV-VIS and X-ray crystallographic approaches. X-ray diffraction analysis shows that the compound (1) crystallizes in triclinic crystal lattice with the Pbar1 space group and diffused to form multi-layered structure due to non-covalent interactions such as intramolecular hydrogen bonding (H.B). In addition to experimental investigation, density functional theory (DFT) calculation with M06-2X/6-31G(d,p) and B3LYP/6-31G(d,p) level of theories was performed on compound (1) to obtain optimized geometry, spectroscopic and electronic properties. DFT optimized geometry shows good agreement with the experimental XRD structure. The hyper conjugative interactions and hydrogen bonding network are responsible for the stability of compound (1) as revealed by natural bond orbital (NBO) calculation. Moreover, hydrogen bonding network in the dimer is confirmed by FT-IR and thermodynamic studies showing excellent agreement with XRD and NBO findings. TD-DFT/UV-VIS analysis provides insight that maximum excitation is found in 1 which shows good agreement with experimental UV-VIS result. The global reactivity parameters are calculated using the energies of frontier molecular orbitals also disclosed that the compound is more stable might be due to hydrogen bonding network. Experimental and molecular docking studies indicated that this compound has anti-bacterial and anti-diabetic properties. The binding affinity of this compound against the multidrug efflux pump subunit AcrB OS=Escherichia coli (strain K12) and Human Pancreatic Alpha-Amylase is -9.2 and -10.00 kcal/mol which are higher than the control drugs. Pi-Pi, Pi-anaion, amide-pi and pi-alkyl bonds play key role in drug-protein complexes.

Bond strength of self-etch adhesives after saliva contamination at different application steps.

PubMed

Cobanoglu, N; Unlu, N; Ozer, F F; Blatz, M B

2013-01-01

This study evaluated and compared the effect of saliva contamination and possible decontamination methods on bond strengths of two self-etching adhesive systems (Clearfil SE Bond [CSE], Optibond Solo Plus SE [OSE]). Flat occlusal dentin surfaces were created on 180 extracted human molar teeth. The two bonding systems and corresponding composite resins (Clearfil AP-X, Kerr Point 4) were bonded to the dentin under six surface conditions (n=15/group): group 1 (control): primer/bonding/composite; group 2: saliva/drying/primer/bonding/composite; group 3: primer/saliva/rinsing/drying/primer/bonding/composite; group 4: primer/saliva/rinsing/drying/bonding/composite; group 5: primer/bonding (cured)/saliva/rinsing/drying/primer/bonding/composite; group 6: primer/bonding (cured)/saliva/removing contaminated layer with a bur/rinsing/drying/primer/bonding/composite. Shear bond strength was tested after specimens were stored in distilled water at 37°C for 24 hours. One-way analysis of variance and Tukey post hoc tests were used for statistical analyses. For CSE, groups 2, 3, and 4 and for OSE, groups 6, 2, and 4 showed significantly lower bond strengths than the control group (p<0.05). CSE groups 5 and 6 and OSE groups 3 and 5 revealed bond strengths similar to the control. When saliva contamination occurred after light polymerization of the bonding agent, repeating the bonding procedure recovered the bonding capacity of both self-etch adhesives. However, saliva contamination before or after primer application negatively affected their bond strength.

Comparison of the antibacterial activity of different self-etching primers and adhesives.

PubMed

Korkmaz, Yonca; Ozalp, Meral; Attar, Nuray

2008-11-01

The aim of this study was to evaluate the antibacterial effects of different one-step and two-step self-etching primer/adhesives on Streptococcus mutans (S. mutans), Lactobacillus casei (L. casei), and Lactobacillus acidophilus (L. acidophilus). The antibacterial effects of Clearfil Protect Bond Primer and Bonding agent; AdheSE Primer and Bonding agent; Adper Prompt L-Pop; Futurabond NR; Clearfil Tri S Bond; and Cervitec (positive control, 1% chlorhexidine varnish) were tested against standard strains of S. mutans, L. Casei, and L. acidophilus using the disk diffusion method. Standard filter paper disks (n=5) impregnated with 20 microL of each material were prepared. After incubation at 37 masculineC for 48 hours in a 5-10% CO2 atmosphere, the diameter of inhibition zones were measured in millimeters. Data were analyzed using one way analysis of variance (ANOVA) and multivariate analysis of variance (MANOVA). Duncan's Multiple Range Test was used for pairwise comparison. The size of inhibition zones produced by primer/adhesives varied among the brands. AdheSE Primer: S. mutans (20.6+/-1.51); L. casei (14.8+/-1.78); L. acidophilus (11.4+/-0.54). Adper Prompt L-Pop: S. mutans (19.6+/-1.51); L. casei (13.8+/-1.64); L. acidophilus (13.8+/-1.09). Cervitec: S. mutans (23+/-0.00); L. casei (27+/-0.70); L. acidophilus (22.4+/-0.54). Clearfil Protect Bond Primer: S. mutans (17+/-0.00); L. casei (17.6+/-0.54); L. acidophilus (22.4+/-0.54). Futurabond NR was found effective only against S. mutans (14.6+/-1.67). Of all the materials tested, AdheSE Bonding agent, Clearfil Protect Bond Bonding agent, and Clearfil Tri S Bond exhibited no inhibition zone (-) for all bacteria tested. Among the adhesives tested Clearafil Protect Bond Primer based upon monomer methacryloyloxydodecylpyridiniium bromide (MDPB) was found to be the most potent material against L. acidophilus and L. casei. AdheSE Primer and Adper Prompt L-Pop are highly effective against S. mutans. Compared with other adhesive systems, Clearfil Protect Bond Primer (containing MDPB) showed a high antibacterial effect against all microorganizms tested. Two-step, self-etching primer/adhesive system Clearfil Protect Bond might be a suitable choice under minimally invasive restorations. The recently developed one-step, self-etching system Clearfil Tri S Bond showed no antibacterial effect against microorgazims tested.

Thin film solar cells with Si nanocrystallites embedded in amorphous intrinsic layers by hot-wire chemical vapor deposition.

PubMed

Park, Seungil; Parida, Bhaskar; Kim, Keunjoo

2013-05-01

We investigated the thin film growths of hydrogenated silicon by hot-wire chemical vapor deposition with different flow rates of SiH4 and H2 mixture ambient and fabricated thin film solar cells by implementing the intrinsic layers to SiC/Si heterojunction p-i-n structures. The film samples showed the different infrared absorption spectra of 2,000 and 2,100 cm(-1), which are corresponding to the chemical bonds of SiH and SiH2, respectively. The a-Si:H sample with the relatively high silane concentration provides the absorption peak of SiH bond, but the microc-Si:H sample with the relatively low silane concentration provides the absorption peak of SiH2 bond as well as SiH bond. Furthermore, the microc-Si:H sample showed the Raman spectral shift of 520 cm(-1) for crystalline phase Si bonds as well as the 480 cm(-1) for the amorphous phase Si bonds. These bonding structures are very consistent with the further analysis of the long-wavelength photoconduction tail and the formation of nanocrystalline Si structures. The microc-Si:H thin film solar cell has the photovoltaic behavior of open circuit voltage similar to crystalline silicon thin film solar cell, indicating that microc-Si:H thin film with the mixed phase of amorphous and nanocrystalline structures show the carrier transportation through the channel of nanocrystallites.

Effect of zirconia surface treatment using nitric acid-hydrofluoric acid on the shear bond strengths of resin cements

PubMed Central

Kim, Sun Jai; Shim, June Sung

2017-01-01

PURPOSE The aim of this study was to compare the surface roughness of zirconia when using Zircos E etching system (ZSAT), applying a nitric acid-hydrofluoric acid compound as a pretreatment agent, and also to compare the shear bonding strength according to different resin cements. MATERIALS AND METHODS ZSAT, air abrasion, and tribochemical silicacoating were applied on prepared 120 zirconia specimens (10 mm in diameter, 7 mm in height) using CAD/CAM. Each 12 specimens with 4 different resin cements (Panavia F 2.0, Rely X Unicem, Superbond C&B, and Hot bond) were applied to test interfacial bond strength. The statistical analysis was performed using SAS 9.1 (SAS Institute Inc., Cary, NC, USA). The results are as follows: after application of the ZSAT on the zirconia specimens, surface roughness value after 2-hour etching was higher than those after 1- and 3-hour etching on SEM images. RESULTS For Superbond C&B and Rely X Unicem, the specimens treated with ZSAT showed higher shear bond strength values than those treated with air abrasion and tribochemical silicacoating system. Regarding the failure mode of interface over cement and zirconia surface, Rely X Unicem and Hot bond showed cohesive failures and Panavia F 2.0 and Superbond C&B showed mixed failures. CONCLUSION Zircos E etching system in zirconia restoration could increase its shear bond strength. However, its long term success rate and clinical application should be further evaluated. PMID:28435615

XRD, vibrational spectra and quantum chemical studies of an anticancer drug: 6-Mercaptopurine.

PubMed

Kumar, S Suresh; Athimoolam, S; Sridhar, B

2015-07-05

The single crystal of the hydrated anticancer drug, 6-Mercaptopurine (6-MP), has been grown by slow evaporation technique under room temperature. The structure was determined by single crystal X-ray diffraction. The vibrational spectral analysis was carried out using Laser Raman and FT-IR spectroscopy in the range of 3300-100 and 4000-400 cm(-1). The single crystal X-ray studies shows that the crystal packing is dominated by N-H⋯O and O-H⋯N classical hydrogen bonds leading to a hydrogen bonded ensemble. This classical hydrogen bonds were further connected through O-H⋯S hydrogen bond to form two primary ring R4(4)(16) and R4(4)(12) motifs. These two primary ring motifs are interlinked with each other to build a ladder like structure. These ladders are connected through N-H⋯N hydrogen bond along c-axis of the unit cell through chain C(5) motifs. Further, the strength of the hydrogen bonds is studied through vibrational spectral measurements. The shifting of bands due to the intermolecular interactions was also analyzed in the solid crystalline state. Geometrical optimizations of the drug molecule were done by Density Functional Theory (DFT) using the B3LYP function and Hartree-Fock (HF) level with 6-311++G(d,p) basis set. The optimized molecular geometry and computed vibrational spectra are compared with experimental results which show significant agreement. The natural bond orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and intramolecular charge transfer (ICT). The chemical hardness, electro-negativity and chemical potential of the molecule are carried out by HOMO-LUMO plot. In which, the frontier orbitals has lower band gap value indicating the possible pharmaceutical activity of the molecule. Copyright © 2015 Elsevier B.V. All rights reserved.

Microsolvation effect and hydrogen-bonding pattern of taurine-water TA-(H2O)n (n = 1-3) complexes.

PubMed

Dai, Yumei; Wang, Yuhua; Huang, Zhengguo; Wang, Hongke; Yu, Lei

2012-01-01

The microsolvation of taurine (TA) with one, two or three water molecules was investigated by a density functional theory (DFT) approach. Quantum theory of atoms in molecules (QTAIM) analyses were employed to elucidate the hydrogen bond (H-bond) interaction characteristics in TA-(H(2)O)(n) (n = 1-3) complexes. The results showed that the intramolecular H-bond formed between the hydroxyl and the N atom of TA are retained in most TA-(H(2)O)(n) (n = 1-3) complexes, and are strengthened via cooperative effects among multiple H-bonds from n = 1-3. A trend of proton transformation exists from the hydroxyl to the N atom, which finally results in the cleavage of the origin intramolecular H-bond and the formation of a new intramolecular H-bond between the amino and the O atom of TA. Therefore, the most stable TA-(H(2)O)(3) complex becomes a zwitterionic complex rather than a neutral type. A many-body interaction analysis showed that the major contributors to the binding energies for complexes are the two-body energies, while three-body energies and relaxation energies make significant contributions to the binding energies for some complexes, whereas the four-body energies are too small to be significant.

Ab initio modeling of complex amorphous transition-metal-based ceramics.

PubMed

Houska, J; Kos, S

2011-01-19

Binary and ternary amorphous transition metal (TM) nitrides and oxides are of great interest because of their suitability for diverse applications ranging from high-temperature machining to the production of optical filters or electrochromic devices. However, understanding of bonding in, and electronic structure of, these materials represents a challenge mainly due to the d electrons in their valence band. In the present work, we report ab initio calculations of the structure and electronic structure of ZrSiN materials. We focus on the methodology needed for the interpretation and automatic analysis of the bonding structure, on the effect of the length of the calculation on the convergence of individual quantities of interest and on the electronic structure of materials. We show that the traditional form of the Wannier function center-based algorithm fails due to the presence of d electrons in the valence band. We propose a modified algorithm, which allows one to analyze bonding structure in TM-based systems. We observe an appearance of valence p states of TM atoms in the electronic spectra of such systems (not only ZrSiN but also NbO(x) and WAuO), and examine the importance of the p states for the character of the bonding as well as for facilitating the bonding analysis. The results show both the physical phenomena and the computational methodology valid for a wide range of TM-based ceramics.

Bond strength of an alkylene bis(dilactoyl)-methacrylate bone adhesive: a biomechanical evaluation in sheep.

PubMed

Heiss, Christian; Schettler, Nicky; Wenisch, Sabine; Cords, Sven; Schilke, Frank; Lips, Katrin Susanne; Alt, Volker; Schnettler, Reinhard

2010-01-01

The purpose of this study is to assess the mechanical efficacy of an alkylene bis(dilactoyl)-methacrylate-based degradable bone adhesive in 36 sheep. Bone segmentation with osteotomies of the metaphyseal ulna was performed and adhesive was applied into the osteotomy gaps in 18 sheep. The remaining 18 animals served as controls. The segment was subsequently stabilized without any osteosynthesis in all sheep. Six animals of the adhesive group and 6 controls were killed after 21, 42 and 84 days, respectively. Bond strength of the adhesive and quality of fracture healing was studied using biomechanical, histological and radiological methods. There were no significant differences in biomechanical analysis between both groups at any time. However, an increase of in vivo bond strength with the highest stiffness of 102.83 N/mm(2) was observed in the adhesive group after 84 days. In vitro analysis showed non-significant differences in bond strength during polymerization time. Histomorphometric investigations revealed significant differences in osteotomy cross-section area after 84 days, with higher areas of callus in the control. After 84 days the X-ray examinations showed completely bridged gaps in four of six animals in the adhesive and in five animals in the control group. This bone adhesive exhibited good in vivo and in vitro bond strength and mechanical efficiency in both the short and long term without impairment of physiological fracture healing.

In vivo effects of two acidic soft drinks on shear bond strength of metal orthodontic brackets with and without resin infiltration treatment.

PubMed

Hammad, Shaza M; Enan, Enas T

2013-07-01

To evaluate the in vivo effects of two acidic soft drinks (Coca-Cola and Sprite) on the shear bond strength of metal orthodontic brackets with and without resin infiltration treatment. In addition, the enamel surface was evaluated, after debonding, using a scanning electron microscope. Sixty noncarious maxillary premolars, scheduled for extraction in 30 orthodontic patients, were used. Patients were randomly divided into two groups according to the soft drink tested (Coca-Cola or Sprite). In each group, application of resin infiltration (Icon. DMG, Hamburg, Germany) was done on one side only before bonding of brackets. Patients were told to rinse their mouth with their respective soft drink at room temperature for 5 minutes, three times a day for 3 months. Shear bond strength was tested with a universal testing machine. After shearing test, a scanning electron microscope was used to evaluate enamel erosion. Statistical analysis was performed by twoway analysis of variance followed by the least significant difference test. The Coca-Cola group without resin infiltration showed the lowest resistance to shearing forces. Scanning electron micrographs of both groups after resin application showed a significant improvement compared with results without resin use, as the enamel appeared smoother and less erosive. Pretreatment with the infiltrating resin has proved to result in a significant improvement in shear bond strength, regardless of the type of soft drink consumed.

Diffusion Bonding of Silicon Carbide for MEMS-LDI Applications

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay; Shpargel, Tarah P.; Kiser, J. Douglas

2007-01-01

A robust joining approach is critically needed for a Micro-Electro-Mechanical Systems-Lean Direct Injector (MEMS-LDI) application which requires leak free joints with high temperature mechanical capability. Diffusion bonding is well suited for the MEMS-LDI application. Diffusion bonds were fabricated using titanium interlayers between silicon carbide substrates during hot pressing. The interlayers consisted of either alloyed titanium foil or physically vapor deposited (PVD) titanium coatings. Microscopy shows that well adhered, crack free diffusion bonds are formed under optimal conditions. Under less than optimal conditions, microcracks are present in the bond layer due to the formation of intermetallic phases. Electron microprobe analysis was used to identify the reaction formed phases in the diffusion bond. Various compatibility issues among the phases in the interlayer and substrate are discussed. Also, the effects of temperature, pressure, time, silicon carbide substrate type, and type of titanium interlayer and thickness on the microstructure and composition of joints are discussed.

Structural characterization of polysaccharides from bamboo

NASA Astrophysics Data System (ADS)

Kamil, Ruzaimah Nik Mohamad; Yusuf, Nur'aini Raman; Yunus, Normawati M.; Yusup, Suzana

2014-10-01

The alkaline and water soluble polysaccharides were isolate by sequential extractions with distilled water, 60% ethanol containing 1%, 5% and 8% NaOH. The samples were prepared at 60 °C for 3 h from local bamboo. The functional group of the sample were examined using FTIR analysis. The most precipitate obtained is from using 60% ethanol containing 8% NaOH with yield of 2.6%. The former 3 residues isolated by sequential extractions with distilled water, 60% ethanol containing 1% and 5% NaOH are barely visible after filtering with cellulose filter paper. The FTIR result showed that the water-soluble polysaccharides consisted mainly of OH group, CH group, CO indicates the carbohydrate and sugar chain. The sample weight loss was slightly decreased with increasing of temperature.

Improving the accuracy of Density Functional Theory (DFT) calculation for homolysis bond dissociation energies of Y-NO bond: generalized regression neural network based on grey relational analysis and principal component analysis.

PubMed

Li, Hong Zhi; Tao, Wei; Gao, Ting; Li, Hui; Lu, Ying Hua; Su, Zhong Min

2011-01-01

We propose a generalized regression neural network (GRNN) approach based on grey relational analysis (GRA) and principal component analysis (PCA) (GP-GRNN) to improve the accuracy of density functional theory (DFT) calculation for homolysis bond dissociation energies (BDE) of Y-NO bond. As a demonstration, this combined quantum chemistry calculation with the GP-GRNN approach has been applied to evaluate the homolysis BDE of 92 Y-NO organic molecules. The results show that the ull-descriptor GRNN without GRA and PCA (F-GRNN) and with GRA (G-GRNN) approaches reduce the root-mean-square (RMS) of the calculated homolysis BDE of 92 organic molecules from 5.31 to 0.49 and 0.39 kcal mol(-1) for the B3LYP/6-31G (d) calculation. Then the newly developed GP-GRNN approach further reduces the RMS to 0.31 kcal mol(-1). Thus, the GP-GRNN correction on top of B3LYP/6-31G (d) can improve the accuracy of calculating the homolysis BDE in quantum chemistry and can predict homolysis BDE which cannot be obtained experimentally.

The effect of weak interface on transverse properties of a ceramic matrix composite

NASA Technical Reports Server (NTRS)

Shimansky, R. A.; Hahn, H. T.; Salamon, N. J.

1990-01-01

Experimental studies conducted at NASA Lewis on SiC reaction-bonded Si3N4 composite system showed that transverse stiffness and strength were much lower than those predicted from existing analytical models based on good interfacial bonding. It was believed that weakened interfaces were responsible for the decrease in tranverse properties. To support this claim, a two-dimensional FEM analysis was performed for a transverse representative volume element. Specifically, the effect of fiber/matrix displacement compatibility at the interface was studied under both tensile and compressive transverse loadings. Interface debonding was represented using active gap elements connecting the fiber and matrix. The analyses show that the transverse tensile strength and stiffness are best predicted when a debonded interface is assumed for the composite. In fact, the measured properties can be predicted by simply replacing the fibers by voids. Thus, it is found that little or no interfacial bonding exists in the composite, and that an elastic analysis can predict the transverse stiffness and strength.

A novel biomimetic orthodontic bonding agent helps prevent white spot lesions adjacent to brackets.

PubMed

Manfred, Lauren; Covell, David A; Crowe, Jennifer J; Tufekci, Eser; Mitchell, John C

2013-01-01

To compare changes in enamel microhardness adjacent to orthodontic brackets after using bonding agents containing various compositions of bioactive glass compared to a traditional resin adhesive following a simulated caries challenge. Extracted human third molars (n  =  10 per group) had orthodontic brackets bonded using one of four novel bioactive glass (BAG)-containing orthodontic bonding agents (BAG-Bonds) or commercially available Transbond-XT. The four new adhesives contained BAG in varying percentages incorporated into a traditional resin monomer mixture. Teeth were cycled through low-pH demineralizing and physiologic-pH remineralizing solutions once each day over 14 days. Microhardness was measured on longitudinal sections of the teeth 100, 200, and 300 µm from the bracket edge and beneath the brackets, at depths of 25 to 200 µm from the enamel surface. Normalized hardness values were compared using three-way analysis of variance. Significantly less reduction in enamel microhardness was found with the experimental adhesives at depths of 25 and 50 µm at all distances from the bracket edge. In all groups, there were no significant changes in enamel microhardness past 125-µm depth. Results varied with the different BAG-Bonds, with 81BAG-Bond showing the smallest decrease in enamel microhardness. The BAG-Bonds tested in this study showed a reduction in the amount of superficial enamel softening surrounding orthodontic brackets compared to a traditional bonding agent. The results indicate that clinically, BAG-Bonds may aid in maintaining enamel surface hardness, therefore helping prevent white spot lesions adjacent to orthodontic brackets.

Recycling stainless steel orthodontic brackets with Er:YAG laser - An environmental scanning electron microscope and shear bond strength study.

PubMed

Chacko, Prince K; Kodoth, Jithesh; John, Jacob; Kumar, Kishore

2013-07-01

TO DETERMINE THE EFFICIENCY OF ERBIUM: Yttrium aluminum garnet (Er:YAG) laser with Environmental Scanning Electron Microscope (ESEM) and shear bond strength analysis as a method of recycling stainless steel orthodontic brackets and compare with other methods of recycling. Eighty samples of extracted premolar teeth bonded to SS brackets were tested for rebonded shear bond strength after recycling by four methods and compared with a control group of 20 samples. These 80 samples were randomized into four groups which were recycled by four methods, namely, sandblasting, thermal method, adhesive grinding by tungsten carbide bur, and Er: YAG laser method. After recycling, ESEM and shear bond strength analysis were used to analyze the efficiency of the recycling methods. ER: YAG laser group was found to be having the greatest bond strength among the recycled brackets (8.33±2.51 followed by the sandblasting at 6.12±1.12 MPa, thermal and electropolishing at 4.44±0.95 MPa, and lastly the adhesive grinding method at 3.08±1.07 MPa. The shear bond strength of Er: YAG laser group was found to be having no statistically significant difference with that of the control group (P>0.05 and had statistical signifance with sandblasting, thermal and electropolishing and adhesive grinding groups at P>0.001. ESEM analysis showed complete removal of adhesive from the brackets recycled with Er: YAG laser which mimicked that of the control group. ER: YAG laser (2940 nm) was found to be the most efficient method for recycling, followed by the sandblasting, thermal, and the tungsten carbide methods, which had the least shear bond strength value and is not fit for clinical usage.

Pulsed laser ablation of borax target in vacuum and hydrogen DC glow discharges

NASA Astrophysics Data System (ADS)

Kale, A. N.; Miotello, A.; Mosaner, P.

2006-09-01

The aim of our experiment was to produce a material with B sbnd H bonds for applications in hydrogen storage and generation. By using KrF excimer laser ( λ = 248 nm) ablation of borax (Na 2B 4O 7) target, thin films were deposited on KBr and silicon substrates. Ablation was performed both in vacuum and in hydrogen atmosphere. DC glow discharge technique was utilized to enhance hydrogen gas ionization. Experiments were performed using laser fluence from 5 to 20 J/cm 2. Films were deposited under gas pressure of 1 × 10 -5 to 5 × 10 -2 mbar and substrate temperatures of 130-450 °C. Scanning electron microscopy analysis of films showed presence of circular particulates. Film thickness, roughness and particulates number increased with increase in laser fluence. Energy dispersive X-ray spectroscopy analysis shows that sodium content in the particulates is higher than in the target. This effect is discussed in terms of atomic arrangements (both at surface and bulk) in systems where ionic and covalent bonds are present and by looking at the increased surface/bulk ratio of the particulates with respect to the deposited films. The Fourier transform infrared spectroscopy measurements showed presence of B sbnd O stretching and B sbnd O sbnd B bending bonds. Possible reasons for absence of B sbnd H bonds are attributed to binding enthalpy of the competing molecules.

In vitro longevity of bonding properties of universal adhesives to dentin.

PubMed

Muñoz, M A; Luque-Martinez, I; Malaquias, P; Hass, V; Reis, A; Campanha, N H; Loguercio, A D

2015-01-01

To evaluate the immediate and 6-month resin-dentin bond strength (μTBS) and nanoleakage (NL) of universal adhesives that contain or do not contain methacryloyloxydecyl dihydrogen phosphate (MDP) and are used in the etch-and-rinse and self-etch strategies. Forty caries-free extracted third molars were divided into eight groups for μTBS (n=5). The groups were bonded with the Clearfil SE Bond (CSE) and Adper Single Bond 2 (SB) as controls; Peak Universal, self-etch (PkSe) and etch-and rinse (PkEr); Scotchbond Universal Adhesive, self-etch (ScSe) and etch-and-rinse (ScEr); and All Bond Universal, self-etch (AlSe) and etch-and-rinse (AlEr). After composite restorations, specimens were longitudinally sectioned to obtain resin-dentin bonded sticks (0.8 mm(2)). The μTBS of the specimens was tested immediately (IM) or after 6 months of water storage (6M) at 0.5 mm/min. Some sticks at each storage period were immersed in silver nitrate and photo developed, and the NL was evaluated with scanning electron microscopy. Data were analyzed with two-way repeated-measures analysis of variance and Tukey test (α=0.05). At the IM period, PkSe and PkEr showed μTBS similar to the control adhesives (p>0.05) but increased NL pattern and lower μTBS after 6M (p<0.05). ScSe and ScEr showed intermediary μTBS values at the IM period but remained stable after 6 months (p>0.05). AlSe showed the lowest μTBS (p<0.05), but μTBS and NL remained stable after 6M (p>0.05). AlEr showed higher IM μTBS but showed higher degradation after 6M (p<0.05). Universal adhesives that contain MDP showed higher and more stable μTBS with reduced NL at the interfaces after 6 months of water storage.

DFT and TD-DFT computation of charge transfer complex between o-phenylenediamine and 3,5-dinitrosalicylic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Afroz, Ziya; Zulkarnain,; Ahmad, Afaq, E-mail: afaqahmad3@gmail.com

2016-05-23

DFT and TD-DFT studies of o-phenylenediamine (PDA), 3,5-dinitrosalicylic acid (DNSA) and their charge transfer complex have been carried out at B3LYP/6-311G(d,p) level of theory. Molecular geometry and various other molecular properties like natural atomic charges, ionization potential, electron affinity, band gap, natural bond orbital (NBO) and frontier molecular analysis have been presented at same level of theory. Frontier molecular orbital and natural bond orbital analysis show the charge delocalization from PDA to DNSA.

The effect of Er:YAG laser irradiation on the bond stability of self-etch adhesives at different dentin depths.

PubMed

Karadas, Muhammet; Çağlar, İpek

2017-07-01

The aim of this study was to evaluate the effect of Er:YAG laser irradiation on the micro-shear bond strength of self-etch adhesives to the superficial dentin and the deep dentin before and after thermocycling. Superficial dentin and deep dentin surfaces were prepared by flattening of the occlusal surfaces of extracted human third molars. The deep or superficial dentin specimens were randomized into three groups according to the following surface treatments: group I (control group), group II (Er:YAG laser; 1.2 W), and group III (Er:YAG laser; 0.5 W). Clearfil SE Bond or Clearfil S 3 Bond was applied to each group's dentin surfaces. After construction of the composite blocks on the dentin surface, the micro-shear bond testing of each adhesive was performed at 24 h or after 15,000 thermal cycles. The data were analyzed using a univariate analysis of variance and Tukey's test (p < 0.05). Laser irradiation in superficial dentin did not significantly affect bond strength after thermocycling (p > 0.05). However, deep-dentin specimens irradiated with laser showed significantly higher bond strengths than did control specimens after thermocycling (p < 0.05). Thermocycling led to significant deterioration in the bond strengths of all deep-dentin groups. The stable bond strength after thermocycling was measured for all of the superficial-dentin groups. No significant difference was found between the 0.5 and 1.2 W output power settings. In conclusion, the effect of laser irradiation on the bond strength of self-etch adhesives may be altered by the dentin depth. Regardless of the applied surface treatment, deep dentin showed significant bond degradation.

Evaluation of bonded boron/epoxy doublers for commercial aircraft aluminum structures

NASA Technical Reports Server (NTRS)

Belason, Bruce; Rutherford, Paul; Miller, Matthew; Raj, Shreeram

1994-01-01

An 18 month laboratory test and stress analysis program was conducted to evaluate bonded boron/epoxy doublers for repairing cracks on aluminum aircraft structures. The objective was to obtain a core body of substantiating data which will support approval for use on commercial transports of a technology that is being widely used by the military. The data showed that the doublers had excellent performance.

A slow-forming isopeptide bond in the structure of the major pilin SpaD from Corynebacterium diphtheriae has implications for pilus assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Hae Joo; Paterson, Neil G.; Kim, Chae Un

2014-05-01

Two crystal structures of the major pilin SpaD from C. diphtheriae have been determined at 1.87 and 2.5 Å resolution. The N-terminal domain is found to contain an isopeptide bond that forms slowly over time in the recombinant protein. Given its structural context, this provides insight into the relationship between internal isopeptide-bond formation and pilus assembly. The Gram-positive organism Corynebacterium diphtheriae, the cause of diphtheria in humans, expresses pili on its surface which it uses for adhesion and colonization of its host. These pili are covalent protein polymers composed of three types of pilin subunit that are assembled by specificmore » sortase enzymes. A structural analysis of the major pilin SpaD, which forms the polymeric backbone of one of the three types of pilus expressed by C. diphtheriae, is reported. Mass-spectral and crystallographic analysis shows that SpaD contains three internal Lys–Asn isopeptide bonds. One of these, shown by mass spectrometry to be located in the N-terminal D1 domain of the protein, only forms slowly, implying an energy barrier to bond formation. Two crystal structures, of the full-length three-domain protein at 2.5 Å resolution and of a two-domain (D2-D3) construct at 1.87 Å resolution, show that each of the three Ig-like domains contains a single Lys–Asn isopeptide-bond cross-link, assumed to give mechanical stability as in other such pili. Additional stabilizing features include a disulfide bond in the D3 domain and a calcium-binding loop in D2. The N-terminal D1 domain is more flexible than the others and, by analogy with other major pilins of this type, the slow formation of its isopeptide bond can be attributed to its location adjacent to the lysine used in sortase-mediated polymerization during pilus assembly.« less

Effects of ultraviolet irradiation on bonding strength between Co-Cr alloy and citric acid-crosslinked gelatin matrix.

PubMed

Inoue, Motoki; Sasaki, Makoto; Katada, Yasuyuki; Taguchi, Tetsushi

2014-02-01

Novel techniques for creating a strong bond between polymeric matrices and biometals are required. We immobilized polymeric matrices on the surface of biometal for drug-eluting stents through covalent bond. We performed to improve the bonding strength between a cobalt-chromium alloy and a citric acid-crosslinked gelatin matrix by ultraviolet irradiation on the surface of cobalt-chromium alloy. The ultraviolet irradiation effectively generated hydroxyl groups on the surface of the alloy. The bonding strength between the gelatin matrix and the alloy before ultraviolet irradiation was 0.38 ± 0.02 MPa, whereas it increased to 0.48 ± 0.02 MPa after ultraviolet irradiation. Surface analysis showed that the citric acid derivatives occurred on the surface of the cobalt-chromium alloy through ester bond. Therefore, ester bond formation between the citric acid derivatives active esters and the hydroxyl groups on the cobalt-chromium alloy contributed to the enhanced bonding strength. Ultraviolet irradiation and subsequent immobilization of a gelatin matrix using citric acid derivatives is thus an effective way to functionalize biometal surfaces.

Natural bond orbital analysis in the ONETEP code: applications to large protein systems.

PubMed

Lee, Louis P; Cole, Daniel J; Payne, Mike C; Skylaris, Chris-Kriton

2013-03-05

First principles electronic structure calculations are typically performed in terms of molecular orbitals (or bands), providing a straightforward theoretical avenue for approximations of increasing sophistication, but do not usually provide any qualitative chemical information about the system. We can derive such information via post-processing using natural bond orbital (NBO) analysis, which produces a chemical picture of bonding in terms of localized Lewis-type bond and lone pair orbitals that we can use to understand molecular structure and interactions. We present NBO analysis of large-scale calculations with the ONETEP linear-scaling density functional theory package, which we have interfaced with the NBO 5 analysis program. In ONETEP calculations involving thousands of atoms, one is typically interested in particular regions of a nanosystem whilst accounting for long-range electronic effects from the entire system. We show that by transforming the Non-orthogonal Generalized Wannier Functions of ONETEP to natural atomic orbitals, NBO analysis can be performed within a localized region in such a way that ensures the results are identical to an analysis on the full system. We demonstrate the capabilities of this approach by performing illustrative studies of large proteins--namely, investigating changes in charge transfer between the heme group of myoglobin and its ligands with increasing system size and between a protein and its explicit solvent, estimating the contribution of electronic delocalization to the stabilization of hydrogen bonds in the binding pocket of a drug-receptor complex, and observing, in situ, the n → π* hyperconjugative interactions between carbonyl groups that stabilize protein backbones. Copyright © 2012 Wiley Periodicals, Inc.

Probing for and Quantifying Agonist Hydrogen Bonds in α6β2 Nicotinic Acetylcholine Receptors.

PubMed

Post, Michael R; Lester, Henry A; Dougherty, Dennis A

2017-04-04

Designing subtype-selective agonists for neuronal nicotinic acetylcholine receptors is a challenging and significant goal aided by intricate knowledge of each subtype's binding patterns. We previously reported that in α6β2 receptors, acetylcholine makes a functional cation-π interaction with Trp149, but nicotine and TC299423 do not, suggesting a distinctive binding site. This work explores hydrogen binding at the backbone carbonyl associated with α6β2 Trp149. Substituting residue i + 1, Thr150, with its α-hydroxy analogue (Tah) attenuates the carbonyl's hydrogen bond accepting ability. At α6(T150Tah)β2, nicotine shows a 24-fold loss of function, TC299423 shows a modest loss, and acetylcholine shows no effect. Nicotine was further analyzed via a double-mutant cycle analysis utilizing N'-methylnicotinium, which indicated a hydrogen bond in α6β2 with a ΔΔG of 2.6 kcal/mol. Thus, even though nicotine does not make the conserved cation-π interaction with Trp149, it still makes a functional hydrogen bond to its associated backbone carbonyl.

Electron transfer dynamics of bistable single-molecule junctions.

PubMed

Danilov, Andrey V; Kubatkin, Sergey E; Kafanov, Sergey G; Flensberg, Karsten; Bjørnholm, Thomas

2006-10-01

We present transport measurements of single-molecule junctions bridged by a molecule with three benzene rings connected by two double bonds and with thiol end-groups that allow chemical binding to gold electrodes. The I-V curves show switching behavior between two distinct states. By statistical analysis of the switching events, we show that a 300 meV mode mediates the transition between the two states. We propose that breaking and reformation of a S-H bond in the contact zone between molecule and electrode explains the observed bistability.

Retention Strength of PMMA/UDMA-Based Crowns Bonded to Dentin: Impact of Different Coupling Agents for Pretreatment

PubMed Central

Stawarczyk, Bogna; Teuss, Simona; Eichberger, Marlis; Roos, Malgorzata; Keul, Christine

2015-01-01

Computer aided design/computer aided manufacturing (CAD/CAM) polymers for long-term dental restorations benefit from enhanced mechanical properties. However, the quantification of their bonding properties on teeth is lacking. Therefore, the aim of this study was to determine the retention strength (RS) of differently pretreated new developed polymethylmethacrylate/urethanedimethacrylate-based CAD/CAM polymer bonded on dentin. In summary, 120 human caries-free molars were prepared, and polymeric crowns were milled and pretreated (n = 20): visio.link (VL), Scotchbond Universal (SU), Monobond Plus/Heliobond (MH), Margin Bond (MB), Margin Bond mixed with acetone (1:1) (MBA) or not pretreated (CG). Half of the specimens were cemented using Variolink II and the other half with RelyX Ultimate. Specimens were stored for 24 h in distilled water and thermal cycled (5000 ×, 5 °C/55 °C). The retention load was measured and failure types were defined. RS was calculated and analyzed using both two- and one-way ANOVA with a post-hoc Scheffé-test, unpaired t-test, Kaplan–Meier with Breslow–Gehan test and chi-squared test (p < 0.05). Crowns bonded using RelyX Ultimate showed higher RS than those bonded using Variolink II. The pretreatment showed no impact on the RS. However, survival analysis within Variolink II found an impact of pretreatment. The median RS for MH was the lowest and statistically different from MB, MBA and CG. For Variolink II MH had the poorest survival as the estimated cumulative failure function of the debonded crown increased very quickly with increasing TBS. Within the RelyX Ultimate groups, no significant differences were determined. The newly developed CAD/CAM polymer showed the highest bonding properties after cementation using RelyX Ultimate. PMID:28793651

Identification of non-classical C-H···M interactions in early and late transition metal complexes containing the CH(ArO)3 ligand.

PubMed

Lein, Matthias; Harrison, John A; Nielson, Alastair J

2013-08-14

The fully optimised DFT structure of the d(0) complex [{CH(ArO)3}Ti(NEt2)] (2) at the B3LYP level compares well with the distorted tetrahedral geometry shown by the X-ray crystal structure. QTAIM analysis of the electron density associated with the C-H···Ti interaction shows a well defined bond critical point, a bond path between the hydrogen and titanium centres and a negative value for the energy density indicative of covalency. A natural bond orbital (NBO) picture of the interaction shows that the C-H σ bond electron density donates to a d hybrid orbital on the metal in a linear fashion. Calculated IR and NMR data for the components of the interaction are consistent with experiment. The computed structures for [{CH(ArO)3}Ti(OPh)] (3), [{CH(ArO)3}Zr(NEt2)] (4), [{CH(ArO)3}Hf(NEt2)] (5), show tetrahedral geometries and QTAIM and NBO properties similar to (2). [{CH(ArO)3}Mo(NEt2)] (6) shows distortion of the tripodal ligand and a reduced C-H···M bond angle with properties more consistent with a C-H···M side-on donor interaction. In [{CH(ArO)3}Fe(NEt2)] (7) the C-H···M bond angle is linear and involves a donor interaction. An energy minimised structure maintaining the three fold coordination to the tripodal ligand was not obtained for [{CH(ArO)3}Ni(NEt2)](2-) but changing from a diethyl amide ligand to phenolato gave energy minimised [{CH(ArO)3}Ni(OPh)](2-) (8). This structure shows a distorted square planar geometry with a substantially bent phenoxo ligand and a near linear C-H···M covalent interaction with donor and back bonding properties. The work shows that linear C-H···M interactions can have both agostic and weak hydrogen bond-like covalency.

Spectroscopic study of uracil, 1-methyluracil and 1-methyl-4-thiouracil: Hydrogen bond interactions in crystals and ab-initio molecular dynamics

NASA Astrophysics Data System (ADS)

Brela, Mateusz Z.; Boczar, Marek; Malec, Leszek M.; Wójcik, Marek J.; Nakajima, Takahito

2018-05-01

Hydrogen bond networks in uracil, 1-methyluracil and 1-methyl-4-thiouracil were studied by ab initio molecular dynamics as well as analysis of the orbital interactions. The power spectra calculated by ab initio molecular dynamics for atoms involved in hydrogen bonds were analyzed. We calculated spectra by using anharmonic approximation based on the autocorrelation function of the atom positions obtained from the Born-Oppenheimer simulations. Our results show the differences between hydrogen bond networks in uracil and its methylated derivatives. The studied methylated derivatives, 1-methyluracil as well as 1-methyl-4-thiouracil, form dimeric structures in the crystal phase, while uracil does not form that kind of structures. The presence of sulfur atom instead oxygen atom reflects weakness of the hydrogen bonds that build dimers.

In-Depth Characterization of Protein Disulfide Bonds by Online Liquid Chromatography-Electrochemistry-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Switzar, Linda; Nicolardi, Simone; Rutten, Julie W.; Oberstein, Saskia A. J. Lesnik; Aartsma-Rus, Annemieke; van der Burgt, Yuri E. M.

2016-01-01

Disulfide bonds are an important class of protein post-translational modifications, yet this structurally crucial modification type is commonly overlooked in mass spectrometry (MS)-based proteomics approaches. Recently, the benefits of online electrochemistry-assisted reduction of protein S-S bonds prior to MS analysis were exemplified by successful characterization of disulfide bonds in peptides and small proteins. In the current study, we have combined liquid chromatography (LC) with electrochemistry (EC) and mass analysis by Fourier transform ion cyclotron resonance (FTICR) MS in an online LC-EC-MS platform to characterize protein disulfide bonds in a bottom-up proteomics workflow. A key advantage of a LC-based strategy is the use of the retention time in identifying both intra- and interpeptide disulfide bonds. This is demonstrated by performing two sequential analyses of a certain protein digest, once without and once with electrochemical reduction. In this way, the "parent" disulfide-linked peptide detected in the first run has a retention time-based correlation with the EC-reduced peptides detected in the second run, thus simplifying disulfide bond mapping. Using this platform, both inter- and intra-disulfide-linked peptides were characterized in two different proteins, ß-lactoglobulin and ribonuclease B. In order to prevent disulfide reshuffling during the digestion process, proteins were digested at a relatively low pH, using (a combination of) the high specificity proteases trypsin and Glu-C. With this approach, disulfide bonds in ß-lactoglobulin and ribonuclease B were comprehensively identified and localized, showing that online LC-EC-MS is a useful tool for the characterization of protein disulfide bonds.

Hydrogen-bonding A(LS)2-type low-molecular-mass gelator and its thermotropic mesomorphic behavior.

PubMed

Hou, Qiufei; Wang, Shichao; Zang, Libin; Wang, Xiaoliang; Jiang, Shimei

2009-10-15

A unique cholesterol-based A(LS)2-type gelator, which is a hydrogen-bonding complex based on an ALS-type non-gelator molecule 3-cholesteryl 4-(trans-2-(4-pyridinyl)vinyl)phenyl succinate and a counterpart 3-cholesteryloxycarbonylpropanoic acid, shows strong gelation ability in alcohol and aromatic solvents. The formed gel has a high Tg at low gelation concentration, and its xerogel shows fibrillar microstructure revealed by scanning electron microscopy (SEM). FTIR confirms the existence of intermolecular hydrogen bond in the gelator, and X-ray diffraction (XRD) analysis reveals that the gelator possesses a folded conformation in gel and self-assembles into the fibrillar structure mainly by van der Waals interaction between cholesteryl moieties of the gelator. Further more, the thermotropic behavior of the xerogel is studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), which shows typical optical textures of liquid crystals.

Assessment of psychometric properties of the Postpartum Bonding Questionnaire (PBQ) in Spanish mothers.

PubMed

Garcia-Esteve, Lluïsa; Torres, Anna; Lasheras, Gracia; Palacios-Hernández, Bruma; Farré-Sender, Borja; Subirà, Susana; Valdés, Manuel; Brockington, Ian Fraser

2016-04-01

The Postpartum Bonding Questionnaire (PBQ) was developed to assess mother-infant bonding disturbances in the postpartum period. The aim of this study was to examine the psychometric properties of the Spanish version of the PBQ in a sample of Spanish postpartum women. Eight hundred forty mothers were recruited in the postpartum visit (4-6 weeks after delivery): 513 from a gynecology unit (forming the general population sample) and 327 mothers from a perinatal psychiatry program (forming the clinical sample). All women were assessed by means of the Edinburgh Postnatal Depression Scale (EPDS) and the PBQ. Neither the original four-factor structure nor alternative structures (Reck et al. 2006; Wittkowski et al. 2010) were replicated by the confirmatory factor analyses. An exploratory factor analysis showed a four-factor solution. The Schmid-Leiman transformation found a general factor that accounted for 61% of the variance of the PBQ. Bonding impairment showed higher associations with depressive symptomatology in both samples. The Spanish version of the PBQ showed adequate psychometric properties for use with clinical and general populations of Spanish postpartum women. The results suggest that the PBQ could be summarized by a general factor and confirm the utility of the use of the total score for detecting bonding impairment.

Theoretical investigations on the structure and properties of p-n-alkoxy benzoic acid based liquid crystals

NASA Astrophysics Data System (ADS)

Subhapriya, P.; Dhanapal, V.; Sadasivam, K.; Vijayanand, P. S.

2016-05-01

The present study focused on the structural conformations, alkoxy chain lengths and mesogenic properties of two mole of alkoxy benzoic acid(nOBA) and one mole of suberic acid (SA) hydrogen bonded (nOBASA) complexes (n=8 to 10) by density functional theory (DFT) calculations and the Fourier Transform Infrared (FT-IR) spectrum. The intermolecular hydrogen bond formation was confirmed by the optimized geometric bond lengths and bond angles obtained by computation. Using the natural bond orbital (NBO) analysis, the stability of the molecule arising from hyper conjugative interactions and charge delocalization has been analyzed. Results obtained shows that the charge in electron density (ED) in σ*and π* antibonding orbital and second order delocalization energies E(2) authorizes the occurrence of intermolecular charge transfer. The molecular electrostatic potential (MEP) surface map is plotted over the optimized geometry of the molecule to obtain the chemical reactivity of the molecule. From the local charge distributions, the mesomorphic behavior and the nematic phase stabilities for each of the molecule have been predicted. Finally the calculated result is applied to simulated infrared spectra of 8OBASA mesogens which shows good agreement with the observed spectra. The comparison of the theoretical results obtained with the experimental ones shows the reliability of this DFT method.

[Effect of a nano hydroxyapatite desensitizing paste application on dentin bond strength of three self-etch adhesive systems].

PubMed

Pei, D D; Liu, S Y; Yang, H Y; Gan, J; Huang, C

2017-05-09

Objective: To evaluate a nano-hydroxyapatite (nano-HA) desensitizing paste application on the bond strength of three self-etch adhesives. Methods: Three dentin specimens of about 1 mm thick were cut from two teeth. Scanning electron microscope (SEM) was used to evaluate the dentin surfaces without treatment, after citric acid treatment and after nano-HA treatment. Thirty-six intact third molars extracted for surgical reasons were cut to remove the occlusal enamel with isomet, and then were etched with 1% citric acid for 20 s to simulate the sensitive dentin and divided into two groups randomly using a table of random numbers ( n= 18): the control group (no treatment) and the HA treated group (with nano-HA paste treatment). Each group was divided into three subgroups randomly using a table of random numbers ( n= 6). Subgroup A, B and C was bonded with G-Bond, Clearfil S(3) Bond and FL-Bond Ⅱ according to the manufacture's instruction separately. At 24 h after bonding procedure, and after water storage for 6 months, microtensile bond strength of the specimens was tested and the failure mode was analyzed. Results: SEM obeservation showed that citric acid could open the dentin tubules to set up the sensitive dentin model, and the nano-HA could occlude the dentin tubules effectively. For subgroup A, bonding strength of specimens treated with nano-HA ([41.14±8.91] MPa) was significantly high than that of the control group ([34.27±6.16] MPa) at 24 h after bonding procedure ( P< 0.05). However, after 6 month water ageing, the bonding strength of the control group and the HA treated group showed no significant difference ( P> 0.05). For subgroup B, specimens with nano-HA application showed lower bonding strength ([30.87±6.41] MPa) than that of the control group ([36.73±5.82] MPa) at 24 h after bonding procedure ( P< 0.05), and after 6 month water ageing, the bond strength of nano-HA application ([25.73±6.99] MPa) was also lower than that of the control group ([32.33±5.08] MPa) ( P< 0.05). For subgroup C, the bond strength of the control group and the HA treated group have no significant difference either before or after 6 month water ageing ( P> 0.05). Failure mode analysis showed that more than half of the samples in all groups were adhesive failure. Conclusions: Nano-HA treatment decreased the bond strength of subgroup B, while had no adverse effect on subgroup A and subgroup C.

Neutron structure of human carbonic anhydrase II: a hydrogen-bonded water network "switch" is observed between pH 7.8 and 10.0.

PubMed

Fisher, Zoë; Kovalevsky, Andrey Y; Mustyakimov, Marat; Silverman, David N; McKenna, Robert; Langan, Paul

2011-11-08

The neutron structure of wild-type human carbonic anhydrase II at pH 7.8 has been determined to 2.0 Å resolution. Detailed analysis and comparison to the previously determined structure at pH 10.0 show important differences in the protonation of key catalytic residues in the active site as well as a rearrangement of the H-bonded water network. For the first time, a completed H-bonded network stretching from the Zn-bound solvent to the proton shuttling residue, His64, has been directly observed.

Characterization and Modeling of Fine-Pitch Copper Ball Bonding on a Cu/Low- k Chip

NASA Astrophysics Data System (ADS)

Che, F. X.; Wai, L. C.; Zhang, Xiaowu; Chai, T. C.

2015-02-01

Cu ball bonding faces more challenges than Au ball bonding, for example, excessive deformation of the bond pad and damage of Cu/low- k structures, because of the much greater hardness of Cu free air balls. In this study, dynamic finite-element analysis (FEA) modeling with displacement control was developed to simulate the ball-bonding process. The three-dimensional (3D) FEA simulation results were confirmed by use of stress-measurement data, obtained by use of stress sensors built into the test chip. Stress comparison between two-dimensional (2D) and 3D FEA models showed the 2D plain strain model to be a reasonable and effective model for simulation of the ball-bonding process without loss of accuracy; it also saves computing resources. The 2D FEA model developed was then used in studies of a Cu/low- k chip to find ways of reducing Al bond pad deformation and stresses of low- k structures. The variables studied included Al pad properties, capillary geometry, bond pad design (Al pad thickness, Al pad coated with Ni layer), and the effect of ultrasonic bonding power.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fox, J.W.; Elzinga, M.; Tu, A.T.

The primary structure of myotoxin a, a myotoxin protein from the venom of the North American rattlesnake Crotalus viridis viridis, was determined and the position of the disulfide bonds assigned. The toxin was isolated, carboxymethylated, and cleaved by cyanogen bromide, and the resultant peptides were isolated. The cyanogen bromide peptides were subjected to amino acid sequence analysis. In order to assign the positions of the three disulfide bonds, the native toxin was cleaved sequentially with cyanogen bromide and trypsin. A two peptide unit connected by one disulfide bond was isolated and characterized, and a three-peptide unit connected by two disulfidemore » bonds was isolated. One peptide in the three-peptide unit was identified as Cys-Cys-Lys. In order to establish the linkages between the peptides and Cys-Cys-Lys, one cycle of Edman degradation was carried out such that the Cys-Cys bond was cleaved. Upon isolation and analysis of the cleavage products, the disulfide bonds connecting the three peptides were determined. The positions of the disulfide bridges of myotoxin a were determined to be totally different from those of neurotoxins isolated from snake venoms. The sequence of myotoxin a was compared with the sequences of other snake venom toxins using the computer program RELATE to determine whether myotoxin a is similar to any other types of toxins. From the computer analysis, myotoxin a did not show any close relationship to other toxins except crotamine from the South American rattlesnake Crotalus durissus terrificus.« less

Roles of nonpolar and polar intermolecular interactions in the improvement of the drug loading capacity of PEO-b-PCL with increasing PCL content for two hydrophobic Cucurbitacin drugs.

PubMed

Patel, Sarthak K; Lavasanifar, Afsaneh; Choi, Phillip

2009-09-14

Molecular dynamics (MD) simulation was used to study the roles of nonpolar and polar intermolecular interactions in the improvement of the drug loading capacity of poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PEO-b-PCL) with increasing PCL content for two water insoluble anticancer drugs: Cucurbitacin B (CuB) and Cucurbitacin I (CuI). In particular, random binary mixture models containing 10-12 wt % drug and remaining PEO-b-PCL with three different PCL/PEO (w/w) ratios (0.5, 1, and 2) were used to calculate their Flory-Huggins interaction parameters (chi). The MD simulation results show that, for both CuB and CuI, the computed chi decreases (i.e., affinity increases) with increasing PCL/PEO ratio. Such results are consistent with our experimental observation that increasing the PCL/PEO (w/w) ratio from 1 to 4.8 significantly increases the drug loading capacity of micelles formed by PEO-b-PCL for both drugs. Analysis of the energy data shows that increasing affinity (loading) at higher PCL/PEO ratio is attributed to the increase in favorable polar interactions and to the formation of additional hydrogen bonds (H-bonds) between the drugs and the PCL block rather than to the increase in the hydrophobic characteristics of the diblock copolymer as one would normally expect. In fact, the nonpolar intermolecular interactions became more unfavorable at higher PCL/PEO ratio. Analysis of the radial distribution functions of the model mixtures indicates that at high PCL/PEO ratio, multiple H-bond sites on the PCL block interacted with single H-bond sites on the drug molecules. However, at low PCL/PEO ratio, only single H-bonds formed between various H-bond sites on the drug molecules and those of the PCL and PEO blocks. It seems that formation of H-bonds between multiple H-bond sites on the PCL block and single H-bond sites on the drug molecules is responsible for inducing drug/PEO-b-PCL affinity. The finding also explains the experimental observation that release rates of both drugs decrease with increasing PCL/PEO ratio and that the decrease in the release rate of CuB is more pronounced than that of CuI. Our simulation results show that the number of H-bonds formed between CuB and the PCL block is much higher than that of CuI at high PCL/PEO ratio.

Is group singing special? Health, well-being and social bonds in community-based adult education classes

PubMed Central

Pearce, Eiluned; Launay, Jacques; Machin, Anna; Dunbar, Robin I.M.

2016-01-01

Evidence demonstrates that group singing improves health and well-being, but the precise mechanisms remain unknown. Given that cohesive social networks also positively influence health, we focus on the social aspects of singing, exploring whether improvements in health and well-being are mediated by stronger social bonds, both to the group as a whole (collective-bonding) and to individual classmates (relational-bonding). To do so, seven newly-formed community-based adult education classes (four singing, N=84, and three comparison classes studying creative writing or crafts, N=51) were followed over seven months. Self-report questionnaire data on mental and physical health, well-being, and social bonding were collected at Months 1, 3 and 7. We demonstrate that physical and mental health and satisfaction with life significantly improved over time in both conditions. Path analysis did not show any indirect effects via social bonding of Condition on health and well-being. However, higher collective-bonding at timepoint 3 significantly predicted increased flourishing, reduced anxiety and improved physical health independently of baseline levels. In contrast, relational-bonding showed no such effects, suggesting that it is feeling part of a group that particularly yields health and well-being benefits. Moreover, these results indicate that singing may not improve health and well-being more than other types of activities. Nonetheless, these findings encourage further work to refine our understanding of the social aspects of community-based adult education classes in promoting health, well-being and community cohesion. PMID:27867282

Is group singing special? Health, well-being and social bonds in community-based adult education classes.

PubMed

Pearce, Eiluned; Launay, Jacques; Machin, Anna; Dunbar, Robin I M

Evidence demonstrates that group singing improves health and well-being, but the precise mechanisms remain unknown. Given that cohesive social networks also positively influence health, we focus on the social aspects of singing, exploring whether improvements in health and well-being are mediated by stronger social bonds, both to the group as a whole (collective-bonding) and to individual classmates (relational-bonding). To do so, seven newly-formed community-based adult education classes (four singing, N =84, and three comparison classes studying creative writing or crafts, N =51) were followed over seven months. Self-report questionnaire data on mental and physical health, well-being, and social bonding were collected at Months 1, 3 and 7. We demonstrate that physical and mental health and satisfaction with life significantly improved over time in both conditions. Path analysis did not show any indirect effects via social bonding of Condition on health and well-being. However, higher collective-bonding at timepoint 3 significantly predicted increased flourishing, reduced anxiety and improved physical health independently of baseline levels. In contrast, relational-bonding showed no such effects, suggesting that it is feeling part of a group that particularly yields health and well-being benefits. Moreover, these results indicate that singing may not improve health and well-being more than other types of activities. Nonetheless, these findings encourage further work to refine our understanding of the social aspects of community-based adult education classes in promoting health, well-being and community cohesion.

Shear bond strength of two 2-step etch-and-rinse adhesives when bonding ceramic brackets to bovine enamel.

PubMed

Godard, Marion; Deuve, Benjamin; Lopez, Isabelle; Hippolyte, Marie-Pascale; Barthélemi, Stéphane

2017-09-01

The present study assessed a fracture analysis and compared the shear bond strength (SBS) of two 2-step etch-and-rinse (E&R) adhesives when bonding ceramic orthodontic brackets to bovine enamel. Thirty healthy bovine mandibular incisors were selected and were equally and randomly assigned to 2 experimental groups. Ceramic brackets (FLI Signature Clear ® , RMO) were bonded onto bovine enamel using an adhesive system. In group 1 (n=15), the conventional E&R adhesive (OrthoSolo ® +Enlight ® , Ormco) was used, and in group 2 (n=15), the new E&R adhesive limited to ceramic bracket bonding (FLI ceramic adhesive ® : FLI sealant resin ® +FLI adhesive paste ® , RMO) was used. In order to obtain appropriate enamel surfaces, the vestibular surfaces of mandibular bovine incisors were flat ground. After bonding, all the samples were stored in distilled water at room temperature for 21 days and subsequently tested for SBS, using the Instron ® universal testing machine. The Adhesive Remnant Index (ARI) scores were evaluated. Failure modes were assessed using optical microscopy at magnification ×40. A statistic data analysis was performed using the Mann-Whitney U-test (P<0.05). The test showed a significant difference (P=0.00155) between the two groups for the SBS values. Group 1 had significantly higher SBS values (9.79 to 20.83MPa) than group 2 (8.45 to 13.94MPa). Analysis of the ARI scores revealed that most of the failures occurred at the enamel/adhesive interface. A statistically significant difference was found for the ARI scores between the two groups (P=0.00996). Only two fractured brackets, which remained bonded onto the bovine enamel, were reported. Both occurred in group 1. When bonded to ceramic brackets, FLI ceramic adhesive ® (RMO) was demonstrated to be very predictable and safe for clinical application in enamel bonding, whereas the results obtained with the conventional adhesive system (OrthoSolo ® +Enlight ® , Ormco) were less reproducible and revealed slightly excessive shear bond strength values. Copyright © 2017 CEO. Published by Elsevier Masson SAS. All rights reserved.

Differences and Comparisons of the Properties and Reactivities of Iron(III)–hydroperoxo Complexes with Saturated Coordination Sphere

PubMed Central

Faponle, Abayomi S; Quesne, Matthew G; Sastri, Chivukula V; Banse, Frédéric; de Visser, Sam P

2015-01-01

Heme and nonheme monoxygenases and dioxygenases catalyze important oxygen atom transfer reactions to substrates in the body. It is now well established that the cytochrome P450 enzymes react through the formation of a high-valent iron(IV)–oxo heme cation radical. Its precursor in the catalytic cycle, the iron(III)–hydroperoxo complex, was tested for catalytic activity and found to be a sluggish oxidant of hydroxylation, epoxidation and sulfoxidation reactions. In a recent twist of events, evidence has emerged of several nonheme iron(III)–hydroperoxo complexes that appear to react with substrates via oxygen atom transfer processes. Although it was not clear from these studies whether the iron(III)–hydroperoxo reacted directly with substrates or that an initial O–O bond cleavage preceded the reaction. Clearly, the catalytic activity of heme and nonheme iron(III)–hydroperoxo complexes is substantially different, but the origins of this are still poorly understood and warrant a detailed analysis. In this work, an extensive computational analysis of aromatic hydroxylation by biomimetic nonheme and heme iron systems is presented, starting from an iron(III)–hydroperoxo complex with pentadentate ligand system (L52). Direct C–O bond formation by an iron(III)–hydroperoxo complex is investigated, as well as the initial heterolytic and homolytic bond cleavage of the hydroperoxo group. The calculations show that [(L52)FeIII(OOH)]2+ should be able to initiate an aromatic hydroxylation process, although a low-energy homolytic cleavage pathway is only slightly higher in energy. A detailed valence bond and thermochemical analysis rationalizes the differences in chemical reactivity of heme and nonheme iron(III)–hydroperoxo and show that the main reason for this particular nonheme complex to be reactive comes from the fact that they homolytically split the O–O bond, whereas a heterolytic O–O bond breaking in heme iron(III)–hydroperoxo is found. PMID:25399782

Controlling formation of single-molecule junctions by electrochemical reduction of diazonium terminal groups.

PubMed

Hines, Thomas; Díez-Pérez, Ismael; Nakamura, Hisao; Shimazaki, Tomomi; Asai, Yoshihiro; Tao, Nongjian

2013-03-06

We report controlling the formation of single-molecule junctions by means of electrochemically reducing two axialdiazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in situ between the molecule and gold electrodes. We report a yield enhancement in molecular junction formation as the electrochemical potential of both junction electrodes approach the reduction potential of the diazonium terminal groups. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond.

Understanding metallic bonding: Structure, process and interaction by Rasch analysis

NASA Astrophysics Data System (ADS)

Cheng, Maurice M. W.; Oon, Pey-Tee

2016-08-01

This paper reports the results of a survey of 3006 Year 10-12 students on their understandings of metallic bonding. The instrument was developed based on Chi's ontological categories of scientific concepts and students' understanding of metallic bonding as reported in the literature. The instrument has two parts. Part one probed into students' understanding of metallic bonding as (a) a submicro structure of metals, (b) a process in which individual metal atoms lose their outermost shell electrons to form a 'sea of electrons' and octet metal cations or (c) an all-directional electrostatic force between delocalized electrons and metal cations, that is, an interaction. Part two assessed students' explanation of malleability of metals, for example (a) as a submicro structural rearrangement of metal atoms/cations or (b) based on all-directional electrostatic force. The instrument was validated by the Rasch Model. Psychometric assessment showed that the instrument possessed reasonably good properties of measurement. Results revealed that it was reliable and valid for measuring students' understanding of metallic bonding. Analysis revealed that the structure, process and interaction understandings were unidimensional and in an increasing order of difficulty. Implications for the teaching of metallic bonding, particular through the use of diagrams, critiques and model-based learning, are discussed.

The H2O-CH3F Complex: a Combined Microwave and Infrared Spectroscopic Study Supported by Structure Calculations

NASA Astrophysics Data System (ADS)

Gnanasekar, Sharon Priya; Goubet, Manuel; Arunan, Elangannan; Georges, Robert; Soulard, Pascale; Asselin, Pierre; Huet, T. R.; Pirali, Olivier

2015-06-01

The H2O-CH3F complex could have two geometries, one with a hydrogen bond and one with the newly proposed carbon bond. While in general carbon bonds are weaker than hydrogen bonds, this complex appears to have comparable energies for the two structures. Infrared (IR) and microwave (MW) spectroscopic measurements using, respectively, the Jet-AILES apparatus and the FTMW spectrometer at the PhLAM laboratory, have been carried out to determine the structure of this complex. The IR spectrum shows the formation of the CH3F- H2O hydrogen bonded complex and small red-shifts in OH frequency most probably due to (CH3F)m-(H2O)n clusters. Noticeably, addition of CH_3F in the mixture promotes the formation of small water clusters. Preliminary MW spectroscopic measurements indicate the formation of the hydrogen bonded complex. So far, we have no experimental evidence for the carbon bonded structure. However, calculations of the Ar-CH3F complex show three energetically equivalent structures: a T-shape, a "fluorine" bond and a carbon bond. The MW spectrum of the (Ar)n-CH3F complexes is currently under analysis. Mani, D; Arunan, E. Phys. Chem. Chem. Phys. 2013, 15, 14377. Cirtog, M; Asselin, P; Soulard, P; Tremblay, B; Madebene, B; Alikhani, M. E; Georges, R; Moudens, A; Goubet, M; Huet, T.R; Pirali, O; Roy, P. J. Phys. Chem. A. 2011, 115, 2523 Kassi, S; Petitprez, D; Wlodarczak, G. J. Mol. Struct. 2000, 517-518, 375

Hydrogen bonded supra-molecular framework in inorganic-organic hybrid compounds: Syntheses, structures, and photoluminescent properties

NASA Astrophysics Data System (ADS)

Yan, Li; Liu, Wei; Li, Chuanbi; Wang, Yifei; Ma, Li; Dong, Qinqin

2013-03-01

Two novel compounds constructed from aromatic acid and N-Heterocyclic ligands have been synthesized by hydrothermal reaction: [Cd(mip)(1,8-NDC)(H2O)]2 (1) [mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, 1,8-NDC = naphthalene-1,8-dicarboxylic acid] and Cd(mip)2(NTC)2 (2) [NTC = nicotinic acid]. Compounds 1 and 2 are characterized by elemental analysis, IR, single crystal X-ray diffraction and thermogravimetric analysis (TGA). Single-crystal X-ray investigation reveals that compounds 1-2 are 0 dimensional (0D) structures, and the existence of hydrogen bonds and π-π interactions lead the 0D to 2D novel framework. Hydrogen bonds and π-π interactions are powerful non-covalent intermolecular interactions for directing supra-molecular architectures. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. At room temperature, compound 1 exhibits emission at 449 nm upon excitation at 325 nm, and compound 2 shows a strong emission at 656 nm upon excitation at 350 nm. Fluorescent spectrum displays that compounds 1 and 2 are potential luminescent materials.

Confinement induced binding of noble gas atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khatua, Munmun; Pan, Sudip; Chattaraj, Pratim K., E-mail: pkc@chem.iitkgp.ernet.in

2014-04-28

The stability of Ng{sub n}@B{sub 12}N{sub 12} and Ng{sub n}@B{sub 16}N{sub 16} systems is assessed through a density functional study and ab initio simulation. Although they are found to be thermodynamically unstable with respect to the dissociation of individual Ng atoms and parent cages, ab initio simulation reveals that except Ne{sub 2}@B{sub 12}N{sub 12} they are kinetically stable to retain their structures intact throughout the simulation time (500 fs) at 298 K. The Ne{sub 2}@B{sub 12}N{sub 12} cage dissociates and the Ne atoms get separated as the simulation proceeds at this temperature but at a lower temperature (77 K) itmore » is also found to be kinetically stable. He-He unit undergoes translation, rotation and vibration inside the cavity of B{sub 12}N{sub 12} and B{sub 16}N{sub 16} cages. Electron density analysis shows that the He-He interaction in He{sub 2}@B{sub 16}N{sub 16} is of closed-shell type whereas for the same in He{sub 2}@B{sub 12}N{sub 12} there may have some degree of covalent character. In few cases, especially for the heavier Ng atoms, the Ng-N/B bonds are also found to have some degree of covalent character. But the Wiberg bond indices show zero bond order in He-He bond and very low bond order in cases of Ng-N/B bonds. The energy decomposition analysis further shows that the ΔE{sub orb} term contributes 40.9% and 37.3% towards the total attraction in the He{sub 2} dimers having the same distances as in He{sub 2}@B{sub 12}N{sub 12} and He{sub 2}@B{sub 16}N{sub 16}, respectively. Therefore, confinement causes some type of orbital interaction between two He atoms, which akins to some degree of covalent character.« less

Packed-column capillary electrochromatography and capillary electrochromatography-mass spectrometry using a lithocholic acid stationary phase

PubMed Central

Norton, Dean; Shamsi, Shahab A.

2009-01-01

The preparation and characterization of a novel lithocholic acid (LCA)-based liquid crystalline (LC) stationary phase (SP) suitable for application in packed-column CEC and CEC coupled to MS is described. The extent of bonding reactions of LCA-SP was assessed using 1H-NMR, 13C-NMR and elemental analysis. This characterization is followed by application of the LCA-SP for separation of β-blockers, phenylethylamines (PEAs), polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Using the optimum mobile phase operating conditions (pH 3.0-4.5, 10 mM ammonium acetate, 85% v/v ACN), a comparison of the chromatographic ability of the aminopropyl silica phase vs. the LCA-bonded phase was conducted. The results showed improved selectivity for all test analytes using the latter phase. For example, the CEC-MS of β-blockers demonstrated that the LCA-bonded phase provides separation of six out of seven β-blockers, whereas the amino silica phase provides four peaks of several co-eluting β-blockers. For the CEC-MS analysis of PEAs, the LCA-bonded phase showed improved resolution and different selectivity as compared to the aminopropyl phase. An evaluation of the retention trends for PEAs on both phases suggested that the PEAs were retained based on varying degree of hydroxyl substitution on the aromatic ring. In addition, the MS characterization shows several PEAs fragment in the electrospray either by loss of an alkyl group and/or by loss of H2O. Finally, the LCA-bonded phase displayed significantly higher separation selectivity for PAHs and PCBs as compared to the amino silica phase. PMID:18425746

Shear Bond Strength of Self-etching Adhesives to Cavities Prepared by Diamond Bur or Er,Cr:YSGG Laser and Effect of Prior Acid Etching.

PubMed

Jhingan, Pulkit; Sachdev, Vinod; Sandhu, Meera; Sharma, Karan

2015-12-01

To compare and evaluate shear bond strength of self-etching adhesives bonded to cavities prepared by diamond bur or Er,Cr:YSGG laser and the effect of prior acid etching on shear bond strength. Ninety-six caries-free human premolars were selected and divided into 2 groups depending on mode of cavity preparation (48 teeth each). Cavities were prepared with Er,Cr:YSGG laser in group 1 and diamond burs in an air-turbine handpiece in group 2. Groups 1 and 2 were further subdivided into three subgroups of 8 teeth each, which were bonded with sixth- or seventh-generation adhesives with or without prior acid etching, followed by restoration of all samples with APX Flow. These samples were subjected to shear bond strength testing. In addition, the surface morphology of 24 samples each from groups 1 and 2 was evaluated using SEM. Data were analyzed using the Shapiro-Wilk test, one- and two-way ANOVA, the t-test, and the least significant difference test, which showed that the data were normally distributed (p > 0.05). The shear bond strength of adhesives in cavities prepared by Er,Cr:YSGG laser was significantly higher than in diamond bur-prepared cavities (p < 0.05). SEM analysis showed a smear-layer-free anfractuous surface on laser-ablated teeth, in contrast to conventional bur-prepared teeth. The Er,Cr:YSGG laser-ablated surface proved to be more receptive for adhesion than those prepared by diamond bur irrespective of the bonding agent used. Seventh-generation adhesives yielded higher shear bond strength than did sixth-generation adhesives. Prior acid etching decreased the shear bond strength of self-etching adhesives.

Effects of drying agents on bond strength of etch-and-rinse adhesive systems to enamel immediately after bleaching.

PubMed

Niat, Alireza Boruzi; Yazdi, Fatmeh Maleknejad; Koohestanian, Niloufar

2012-12-01

To determine the effect of drying agents and adhesive solvents on the bond strength of resin composite to enamel immediately after bleaching. Sixty healthy human premolars were bleached using 15% carbamide peroxide gel and randomly divided into three groups according to the immersing solutions applied immediately after bleaching: 70% alcohol, acetone, and distilled water. Each group was randomly divided into two subgroups according to the adhesives that were applied: an alcohol-based adhesive (Single Bond) and an acetone-based adhesive (One Step). By using rubber washers, composite Z100 was placed onto the enamel and shear bond strength was evaluated in a universal testing machine at a crosshead speed of 1 mm/min. The type of failure was also assessed using a stereomicroscope. The data were statistically analyzed by two-way ANOVA and Tukey's post-hoc test (α = 0.05). Fisher's Exact test was used to evaluate differences in the failure modes. Statistical analysis showed that the bond strength of the distilled water groups was significantly lower than that of the other groups, but the bond strengths of the two groups where a drying agent was applied were similar to that of the unbleached group. The acetone-based adhesive (One Step) provided higher bond strength than did the alcohol-based adhesive (Single Bond) (p < 0.05). There was no interaction between the two variables (p > 0.05). Fisher's Exact test showed there was no significant difference in the failure mode of all the experimental groups (p > 0.05). The application of drying agents improves the bond strength of resin composite to bleached enamel. Furthermore, the acetone-based adhesive used in the study had a higher bond strength to bleached enamel than did the alcohol-based adhesive used.

Molecular Dynamic Simulation of Space and Earth-Grown Crystal Structures of Thermostable T1 Lipase Geobacillus zalihae Revealed a Better Structure.

PubMed

Ishak, Siti Nor Hasmah; Aris, Sayangku Nor Ariati Mohamad; Halim, Khairul Bariyyah Abd; Ali, Mohd Shukuri Mohamad; Leow, Thean Chor; Kamarudin, Nor Hafizah Ahmad; Masomian, Malihe; Rahman, Raja Noor Zaliha Raja Abd

2017-09-25

Less sedimentation and convection in a microgravity environment has become a well-suited condition for growing high quality protein crystals. Thermostable T1 lipase derived from bacterium Geobacillus zalihae has been crystallized using the counter diffusion method under space and earth conditions. Preliminary study using YASARA molecular modeling structure program for both structures showed differences in number of hydrogen bond, ionic interaction, and conformation. The space-grown crystal structure contains more hydrogen bonds as compared with the earth-grown crystal structure. A molecular dynamics simulation study was used to provide insight on the fluctuations and conformational changes of both T1 lipase structures. The analysis of root mean square deviation (RMSD), radius of gyration, and root mean square fluctuation (RMSF) showed that space-grown structure is more stable than the earth-grown structure. Space-structure also showed more hydrogen bonds and ion interactions compared to the earth-grown structure. Further analysis also revealed that the space-grown structure has long-lived interactions, hence it is considered as the more stable structure. This study provides the conformational dynamics of T1 lipase crystal structure grown in space and earth condition.

Interplay between Peptide Bond Geometrical Parameters in Nonglobular Structural Contexts

PubMed Central

Esposito, Luciana; De Simone, Alfonso; Vitagliano, Luigi

2013-01-01

Several investigations performed in the last two decades have unveiled that geometrical parameters of protein backbone show a remarkable variability. Although these studies have provided interesting insights into one of the basic aspects of protein structure, they have been conducted on globular and water-soluble proteins. We report here a detailed analysis of backbone geometrical parameters in nonglobular proteins/peptides. We considered membrane proteins and two distinct fibrous systems (amyloid-forming and collagen-like peptides). Present data show that in these systems the local conformation plays a major role in dictating the amplitude of the bond angle N-Cα-C and the propensity of the peptide bond to adopt planar/nonplanar states. Since the trends detected here are in line with the concept of the mutual influence of local geometry and conformation previously established for globular and water-soluble proteins, our analysis demonstrates that the interplay of backbone geometrical parameters is an intrinsic and general property of protein/peptide structures that is preserved also in nonglobular contexts. For amyloid-forming peptides significant distortions of the N-Cα-C bond angle, indicative of sterical hidden strain, may occur in correspondence with side chain interdigitation. The correlation between the dihedral angles Δω/ψ in collagen-like models may have interesting implications for triple helix stability. PMID:24455689

Interplay between peptide bond geometrical parameters in nonglobular structural contexts.

PubMed

Esposito, Luciana; Balasco, Nicole; De Simone, Alfonso; Berisio, Rita; Vitagliano, Luigi

2013-01-01

Several investigations performed in the last two decades have unveiled that geometrical parameters of protein backbone show a remarkable variability. Although these studies have provided interesting insights into one of the basic aspects of protein structure, they have been conducted on globular and water-soluble proteins. We report here a detailed analysis of backbone geometrical parameters in nonglobular proteins/peptides. We considered membrane proteins and two distinct fibrous systems (amyloid-forming and collagen-like peptides). Present data show that in these systems the local conformation plays a major role in dictating the amplitude of the bond angle N-C(α)-C and the propensity of the peptide bond to adopt planar/nonplanar states. Since the trends detected here are in line with the concept of the mutual influence of local geometry and conformation previously established for globular and water-soluble proteins, our analysis demonstrates that the interplay of backbone geometrical parameters is an intrinsic and general property of protein/peptide structures that is preserved also in nonglobular contexts. For amyloid-forming peptides significant distortions of the N-C(α)-C bond angle, indicative of sterical hidden strain, may occur in correspondence with side chain interdigitation. The correlation between the dihedral angles Δω/ψ in collagen-like models may have interesting implications for triple helix stability.

Ignition behavior of an aluminum-bonded explosive (ABX)

NASA Astrophysics Data System (ADS)

Hardin, D. Barrett; Zhou, Min; Horie, Yasuyuki

2017-01-01

We report the results of a study on the ignition behavior of a novel concept and design of a heterogeneous energetic material system called ABX, or aluminum-bonded explosives. The idea is to replace the polymeric binder in polymer-bonded explosives (PBX) with aluminum. The motivation of this study is that a new design may have several desirable attributes, including, among others, electrical conductivity, higher mechanical strength, enhanced integrity, higher energy content, and enhanced thermal stability at elevated temperatures. The analysis carried out concerns the replacement of the Estane binder in a HMX/Estane PBX by aluminum. The HMX volume fraction in the PBX and HMX is approximately 81%. 2D mesoscale simulations are carried out, accounting for elasticity, viscoelasticity, elasto-viscoplasticity, fracture, internal friction, and thermal conduction. Results show that, relative to the PBX, the aluminum bonded explosives (ABX) show significantly less heating and lower ignition sensitivity under the same loading conditions. The findings appear to confirm the expected promise of ABX as a next-generation heterogeneous energetic material system with more desirable attributes.

[Bond strength evaluation of four adhesive systems to dentin in vitro].

PubMed

Xiao, Ximei; Xing, Lu; Xu, Haiping; Jiang, Zhe; Su, Qin

2012-08-01

To compare the adhesive strength and observe the bonding interface. According to statistic analysis and scanning electron microscope (SEM) observation, the resistance capacity of four adhesive systems is evaluated. Prime & Bond NT (PBNT), Tetric N-Bond (TNB), Clearfil SE Bond (CSEB), G Bond (GB) were bonded to the occlusal surfaces and mesial surfaces of third molars respectively. The mesial resins received shear force experiment and the fracture load were recorded. The tensile bond strength (TBS) of the remaining parts were tested. The interfacial configuration were observed under SEM. In the shear bond strength (SBS) experiment, PBNT and TNB showed the best result, but there was no significant difference between them (P>0.05). The SBS of PBNT was stronger than that of CSEB and GB (P<0.05). The SBS of TNB was stronger than that of GB (P<0.05). There was no significant difference between TNB and CSEB (P>0.05). In accordance with the shear force result, the TBS of PBNT and TNB was larger than CSEB and GB (P<0.05). Under SEM, resin tags of PBNT and TNB were longer and slender, the bonding layer was thick. Resin tags of CSEB were shorter, the ones of GB were the fewest and shortest. Compared to self-etching system, total-etching system could reach better bonding strength. There is some connection between the interfacial configuration of adhesives and bond strength of them.

Synthesis of zinc sulfide nanoparticles and their incorporation into poly(hydroxybutyrate) matrix in the formation of a novel nanocomposite

NASA Astrophysics Data System (ADS)

Riaz, Shahina; Raza, Zulfiqar Ali; Majeed, Muhammad Irfan; Jan, Tariq

2018-05-01

In the present study, zinc sulfide (ZnS) nanoparticles (NPs) were successfully synthesized through a modified chemical precipitation protocol and then mediated into poly(hydroxybutyrate) (PHB) matrix to get ZnS/PHB nanocomposite. Mean diameter and zeta potential of ZnS NPs, as determined using dynamic light scattering technique (DLS), were observed to be 53 nm and ‑89 mV, respectively. The structural investigations performed using x-ray diffraction (XRD) technique depicted the phase purity of ZnS NPs exhibiting cubic crystal structure. Fourier transform infrared (FTIR) spectroscopic analysis was conducted to identify the presence or absence of bonding vibrational modes on the surface of synthesized single phase ZnS NPs. The FTIR analysis confirmed the metal to sulphur bond formation by showing the characteristic band at 1123 cm‑1. The UV–vis absorption spectra of ZnS NPs confirmed the synthesis of particles in nanoscale regime showing a λ max of 302 nm. These NPs were then successfully incorporated into PHB matrix to synthesize ZnS/PHB nanocomposite. The synthesis of nanocomposite was confirmed by EDX analysis. The chemical bonding and structural properties of ZnS/PHB nanocomposite were determined by FTIR and XRD analysis, respectively. The FTIR analysis confirmed the synthesis of ZnS/PHB nanocomposite. Moreover, XRD analysis showed that structure of nanocomposite was completely controlled by ZnS NPs as pure PHB exhibited orthorhombic crystal structure while the nanocomposite demonstrated cubic crystal structure of ZnS. Thermal properties of nanocomposite were studied through thermogravimetric analysis revealing that the incorporation of ZnS NPs into PHB matrix lead to enhance heat resistance properties of PHB.

Incorporation of TiO2 nanotubes in a polycrystalline zirconia: Synthesis of nanotubes, surface characterization, and bond strength.

PubMed

Dos Santos, Angélica Feltrin; Sandes de Lucena, Fernanda; Sanches Borges, Ana Flávia; Lisboa-Filho, Paulo Noronha; Furuse, Adilson Yoshio

2018-04-05

Despite numerous advantages such as high strength, the bond of yttria-stabilized zirconia polycrystal (Y-TZP) to tooth structure requires improvement. The purpose of this in vitro study was to evaluate the incorporation of TiO 2 nanotubes into zirconia surfaces and the bond strength of resin cement to the modified ceramic. TiO 2 nanotubes were produced by alkaline synthesis, mixed with isopropyl alcohol (50 wt%) and applied on presintered zirconia disks. The ceramics were sintered, and the surfaces were characterized by confocal laser microscopy, scanning electron microscopy (SEM), and energy-dispersive x-ray spectroscopy (EDS) analysis. For bond strength, the following 6 groups (n=16) were evaluated: without TiO 2 and Single Bond Universal; with TiO 2 nanotubes and Single Bond Universal; without TiO 2 nanotubes and Z-prime; with TiO 2 nanotubes and Z-prime; without TiO 2 and Signum Zirconia Bond; with TiO 2 and Signum Zirconia Bond. After sintering, resin cement cylinders, diameter of 1.40 mm and 1 mm in height, were prepared and polymerized for 20 seconds. Specimens were stored in water at 37°C for 30 days and submitted to a shear test. Data were analyzed by 2-way ANOVA and Tukey honest significant difference (α=.05) tests. EDS analysis confirmed that nanoagglomerates were composed of TiO 2 . The shear bond strength showed statistically significant differences among bonding agents (P<.001). No significant differences were found with the application of nanotubes, regardless of the group analyzed (P=.682). The interaction among the bonding agent factors and addition of nanotubes was significant (P=.025). Nanotubes can be incorporated into zirconia surfaces. However, this incorporation did not improve bond strength. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Composition and properties of the so-called 'diamond-like' amorphous carbon films

NASA Technical Reports Server (NTRS)

Angus, J. C.; Stultz, J. E.; Shiller, P. J.; Macdonald, J. R.; Mirtich, M. J.

1984-01-01

The composition of amorphous 'diamond-like' films made by direct low energy ion beam deposition, R.F. discharge and sputtering was determined by nuclear reaction analysis, IR spectroscopy and microcombustion chemical analysis. The nuclear reaction analysis showed very similar hydrogen depth profiles for all three types of samples. The atomic ratio of hydrogen to carbon was approximately 0.2 at the film surface and rose to approximately 1.0 at a depth of 500 A. The integrated intensity of the C-H stretching band at about 2900 per cm indicates that the amount of chemically bonded hydrogen is less than the total hydrogen content. Combustion analysis confirmed the overall atomic ratio of hydrogen to carbon determined by nuclear reaction analysis. The chemical state of the non-bonded hydrogen was not determined; however, the effective diffusion coefficient computed from the hydrogen depth profile was extremely low. This indicates either that the films are exceedingly impermeable or that the non-bonded hydrogen requires an additional activated step to leave the films, e.g., desorption or chemical reaction.

Influence of stereoelectronic effects on the non-opioid analgesics gaboxadol and gaboxadol hydrochloride: Spectral and DFT study

NASA Astrophysics Data System (ADS)

Leenaraj, D. R.; Joe, I. Hubert

2018-05-01

The stereoelectronic properties of the molecular structure of most stable conformers of gaboxadol and gaboxadol hydrochloride have been studied using DFT/B3P86-LANL2DZ methodology. The energies of stable conformers of gaboxadol and gaboxadol hydrochloride are -494.2689 and -510.0117 hartrees, respectively. The stability of the molecules arising from stereoelectronic interactions, leading to its bioactivity, has been confirmed using natural bond orbital analysis. The natural bond orbital analysis of donor-acceptor (σ→σ* and n→σ*) interactions showed that the stereoelectronic hyperconjugative and anomeric interactions are exhibited in gaboxadol hydrochloride and gaboxadol, respectively. Lengthening of the axial and equatorial C-H bond lengths and natural population analysis support these results. Spectral features of gaboxadol hydrochloride have been explored by the Fourier transform infrared, Raman and Nuclear magnetic resonance spectroscopic techniques combined with density functional theory computations. NH+ … Cl- hydrogen bonding has been noticeable as a broad and strong absorption in the 2800-2400 cm-1 region. Broad peaks obtained by proton NMR are a result of the quadrupole effect of the N+ atom. Docking studies using representative GABA receptor crystal structures revealed that molecules containing azinane and isoxazole cores fit within the ligand binding domains, and the gaboxadol hydrochloride molecule shows the best binding energy with the 3D32 GABA receptor. Also, gaboxadol hydrochloride has obtained a high value of HOMO energy and a narrow HOMO- LUMO energy gap, which enhances reactivity.

Vibrational spectral investigation and natural bond orbital analysis of pharmaceutical compound 7-Amino-2,4-dimethylquinolinium formate - DFT approach

NASA Astrophysics Data System (ADS)

Suresh, D. M.; Amalanathan, M.; Sebastian, S.; Sajan, D.; Hubert Joe, I.; Bena Jothy, V.; Nemec, Ivan

2013-11-01

The molecular geometry, the normal mode frequencies and corresponding vibrational assignments, natural bond orbital analysis and the HOMO-LUMO analysis of 7-Amino-2,4-dimethylquinolinium formate in the ground state were performed by B3LYP levels of theory using the 6-31G(d) basis set. The optimised bond lengths and bond angles are in good agreement with the X-ray data. The vibrational spectra of the title compound which is calculated by DFT method, reproduces vibrational wave numbers and intensities with an accuracy which allows reliable vibrational assignments. The possibility of N-H⋯O hydrogen bonding was identified using NBO analysis. Natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction.

Analysis of the bonding in XH3Cu+ (XB, Al, Ga) complexes

NASA Astrophysics Data System (ADS)

Corral, Inés; Mó, Otilia; Yáñez, Manuel

High-level density functional theory (DFT) calculations on XH3Cu+ (XB, Al, Ga) complexes show that the attachment of the metal cation to the base takes place through agostic-type interactions. These interactions that can be viewed as dative bonds from the σXH bonding orbitals of the base toward low-lying empty 4s orbitals of the metal cation, and back-donations from the lone pairs of the metal into the σ *XH antibonding orbitals of the neutral, are particularly favored when the XH bonds have a high X+δH-δ polarity. Accordingly, the AlH3 and GaH3 Cu+ binding energies are very similar, but much larger than that of BH3. Depopulation of the σXH bonding orbital and the concomitant population of the σ *XH antibonding orbital involved in the agostic interaction result in a significant weakening of the corresponding XH linkages, whose bond length increases and whose stretching frequency appears red-shifted.

Effects of water storage on bond strength and dentin sealing ability promoted by adhesive systems.

PubMed

Cantanhede de Sá, Renata Bacelar; Oliveira Carvalho, Adriana; Puppin-Rontani, Regina Maria; Ambrosano, Glaúcia Maria; Nikaido, Toru; Tagami, Junji; Giannini, Marcelo

2012-12-01

To evaluate the dentin bond strength (BS) and sealing ability (SA) promoted by adhesive systems after 24 h or 6 months of water storage. The tested adhesive systems were: one three-step etch-and-rinse adhesive (Adper Scotchbond Multi-Purpose, SBMP) and three single-step self-etching systems (Adper Easy Bond, Bond Force, and G-Bond Plus). Bovine incisors were used for both evaluations, BS (n = 11) and SA (n = 5). To examine BS, the buccal surface was ground with SiC paper to expose a flat dentin surface. After adhesive application, a block of resin composite was incrementally built up over the bonded surface and sectioned into sticks. These bonded specimens were subjected to microtensile bond strength testing after 24 h and 6 months of water storage using a universal testing machine. For SA analysis, enamel was removed from the buccal surfaces. The teeth were connected to a device to measure the initial SA (10 psi), and the second measurement was taken after treating dentin with EDTA. Afterwards, the adhesive systems were applied to dentin and the SA was re-measured for each adhesive after 24 h and 6 months of water storage. The SA was expressed in terms of percentage of dentinal sealing. BS and SA data were submitted to two-way ANOVA and Tukey's test (α = 0.05). All adhesives showed a reduction of SA after 6 months of water storage. The SA promoted by self-etching adhesives was higher than that of SBMP. No adhesive system showed a reduction of the BS after 6 months. Sealing ability was affected by water storage, while no changes in microtensile bond strength were observed after 6 months of water storage. The single-step self-etching systems showed greater sealing ability than did SBMP, even after 6 months of storage in water.

Spectroscopic and Quantum Chemical Studies on low-spin FeIV=O complexes: Fe-O bonding and its contributions to reactivity

PubMed Central

Decker, Andrea; Rohde, Jan-Uwe; Klinker, Eric J.; Wong, Shaun D.; Que, Lawrence; Solomon, Edward I.

2008-01-01

High valent FeIV=O species are key intermediates in the catalytic cycles of many mononuclear non-heme iron enzymes and have been structurally defined in model systems. Variable temperature magnetic circular dichroism (VT-MCD) spectroscopy has been used to evaluate the electronic structures and in particular the Fe-O bonds of three FeIV=O (S=1) model complexes, [FeIV(O)(TMC)(NCMe)]2+, [FeIV(O)(TMC)(OC(O)CF3)]+, and [FeIV(O)(N4Py)]2+. These complexes are characterized by their strong and covalent Fe-O π-bonds. The MCD spectra show a vibronic progression in the non-bonding → π* excited state, providing the Fe-O stretching frequency and the Fe-O bond length in this excited state and quantifying the π-contribution to the total Fe-O bond. Correlation of these experimental data to reactivity shows that the [FeIV(O)(N4Py)]2+ complex, with the highest reactivity towards hydrogen-atom abstraction among the three, has the strongest Fe-O π-bond. Density Functional calculations were correlated to the data and support the experimental analysis. The strength and covalency of the Fe-O π-bond result in high oxygen character in the important frontier molecular orbitals (FMOs) for this reaction, the unoccupied β-spin d(xz/yz) orbitals, and activates these for electrophilic attack. An extension to biologically relevant FeIV=O (S=2) enzyme intermediates shows that these can perform electrophilic attack reactions along the same mechanistic pathway (π-FMO pathway) with similar reactivity, but also have an additional reaction channel involving the unoccupied α-spin d(z2) orbital (σ-FMO pathway). These studies experimentally probe the FMOs involved in the reactivity of FeIV=O (S=1) model complexes resulting in a detailed understanding of the Fe-O bond and its contributions to reactivity. PMID:18052249

In vitro analysis of riboflavin-modified, experimental, two-step etch-and-rinse dentin adhesive: Fourier transform infrared spectroscopy and micro-Raman studies.

PubMed

Daood, Umer; Swee Heng, Chan; Neo Chiew Lian, Jennifer; Fawzy, Amr S

2015-06-26

To modify two-step experimental etch-and-rinse dentin adhesive with different concentrations of riboflavin and to study its effect on the bond strength, degree of conversion, along with resin infiltration within the demineralized dentin substrate, an experimental adhesive-system was modified with different concentrations of riboflavin (m/m, 0, 1%, 3%, 5% and 10%). Dentin surfaces were etched with 37% phosphoric acid, bonded with respective adhesives, restored with restorative composite-resin, and sectioned into resin-dentin slabs and beams to be stored for 24 h or 9 months in artificial saliva. Micro-tensile bond testing was performed with scanning electron microscopy to analyse the failure of debonded beams. The degree of conversion was evaluated with Fourier transform infrared spectroscopy (FTIR) at different time points along with micro-Raman spectroscopy analysis. Data was analyzed with one-way and two-way analysis of variance followed by Tukey's for pair-wise comparison. Modification with 1% and 3% riboflavin increased the micro-tensile bond strength compared to the control at 24 h and 9-month storage with no significant differences in degree of conversion (P<0.05). The most predominant failure mode was the mixed fracture among all specimens except 10% riboflavin-modified adhesive specimens where cohesive failure was predominant. Raman analysis revealed that 1% and 3% riboflavin adhesives specimens showed relatively higher resin infiltration. The incorporation of riboflavin in the experimental two-step etch-and-rinse adhesive at 3% (m/m) improved the immediate bond strengths and bond durability after 9-month storage in artificial saliva without adversely affecting the degree of conversion of the adhesive monomers and resin infiltration.

In vitro analysis of riboflavin-modified, experimental, two-step etch-and-rinse dentin adhesive: Fourier transform infrared spectroscopy and micro-Raman studies

PubMed Central

Daood, Umer; Swee Heng, Chan; Neo Chiew Lian, Jennifer; Fawzy, Amr S

2015-01-01

To modify two-step experimental etch-and-rinse dentin adhesive with different concentrations of riboflavin and to study its effect on the bond strength, degree of conversion, along with resin infiltration within the demineralized dentin substrate, an experimental adhesive-system was modified with different concentrations of riboflavin (m/m, 0, 1%, 3%, 5% and 10%). Dentin surfaces were etched with 37% phosphoric acid, bonded with respective adhesives, restored with restorative composite–resin, and sectioned into resin–dentin slabs and beams to be stored for 24 h or 9 months in artificial saliva. Micro-tensile bond testing was performed with scanning electron microscopy to analyse the failure of debonded beams. The degree of conversion was evaluated with Fourier transform infrared spectroscopy (FTIR) at different time points along with micro-Raman spectroscopy analysis. Data was analyzed with one-way and two-way analysis of variance followed by Tukey's for pair-wise comparison. Modification with 1% and 3% riboflavin increased the micro-tensile bond strength compared to the control at 24 h and 9-month storage with no significant differences in degree of conversion (P<0.05). The most predominant failure mode was the mixed fracture among all specimens except 10% riboflavin-modified adhesive specimens where cohesive failure was predominant. Raman analysis revealed that 1% and 3% riboflavin adhesives specimens showed relatively higher resin infiltration. The incorporation of riboflavin in the experimental two-step etch-and-rinse adhesive at 3% (m/m) improved the immediate bond strengths and bond durability after 9-month storage in artificial saliva without adversely affecting the degree of conversion of the adhesive monomers and resin infiltration. PMID:25257880

A retrospective survey of the causes of bracket- and tube-bonding failures.

PubMed

Roelofs, Tom; Merkens, Nico; Roelofs, Jeroen; Bronkhorst, Ewald; Breuning, Hero

2017-01-01

To investigate the causes of bonding failures of orthodontic brackets and tubes and the effect of premedicating for saliva reduction. Premedication with atropine sulfate was administered randomly. Failure rate of brackets and tubes placed in a group of 158 consecutive patients was evaluated after a mean period of 67 weeks after bonding. The failure rate in the group without atropine sulfate premedication was 2.4%. In the group with premedication, the failure rate was 2.7%. The Cox regression analysis of these groups showed that atropine application did not lead to a reduction in bond failures. Statistically significant differences in the hazard ratio were found for the bracket regions and for the dental assistants who prepared for the bonding procedure. Premedication did not lead to fewer bracket failures. The roles of the dental assistant and patient in preventing failures was relevant. A significantly higher failure rate for orthodontic appliances was found in the posterior regions.

Spectroscopic study of uracil, 1-methyluracil and 1-methyl-4-thiouracil: Hydrogen bond interactions in crystals and ab-initio molecular dynamics.

PubMed

Brela, Mateusz Z; Boczar, Marek; Malec, Leszek M; Wójcik, Marek J; Nakajima, Takahito

2018-05-15

Hydrogen bond networks in uracil, 1-methyluracil and 1-methyl-4-thiouracil were studied by ab initio molecular dynamics as well as analysis of the orbital interactions. The power spectra calculated by ab initio molecular dynamics for atoms involved in hydrogen bonds were analyzed. We calculated spectra by using anharmonic approximation based on the autocorrelation function of the atom positions obtained from the Born-Oppenheimer simulations. Our results show the differences between hydrogen bond networks in uracil and its methylated derivatives. The studied methylated derivatives, 1-methyluracil as well as 1-methyl-4-thiouracil, form dimeric structures in the crystal phase, while uracil does not form that kind of structures. The presence of sulfur atom instead oxygen atom reflects weakness of the hydrogen bonds that build dimers. Copyright © 2018 Elsevier B.V. All rights reserved.

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part II interfacial bonding analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Steve Xunhu

2015-09-01

Among glass-ceramic compositions modified with a variety of oxidants (AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO 3 and WO 3) only CuO and CoO doped glass-ceramics showed existence of bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The CuO-modified glass-ceramics demonstrate the formation of a continuous layer of strong bonding Cr 2O 3 at the interface in low partial oxygen (PO 2) atmosphere. However, in a local reducing atmosphere, the CuO is preferentially reduced at the surface of glass-ceramic rather than the GC-SS interface for redox. The CoO-modified glass-ceramics demonstrate improved GC-SS bonding. But the low mobility ofmore » Co ++ ions in the GC limited the amount of CoO that can diffuse to and participate in redox at the interface.« less

Near-infrared analysis of hydrogen-bonding in glass- and rubber-state amorphous saccharide solids.

PubMed

Izutsu, Ken-ichi; Hiyama, Yukio; Yomota, Chikako; Kawanishi, Toru

2009-01-01

Near-infrared (NIR) spectroscopic analysis of noncrystalline polyols and saccharides (e.g., glycerol, sorbitol, maltitol, glucose, sucrose, maltose) was performed at different temperatures (30-80 degrees C) to elucidate the effect of glass transition on molecular interaction. Transmission NIR spectra (4,000-12,000 cm(-1)) of the liquids and cooled-melt amorphous solids showed broad absorption bands that indicate random configuration of molecules. Heating of the samples decreased an intermolecular hydrogen-bonding OH vibration band intensity (6,200-6,500 cm(-1)) with a concomitant increase in a free and intramolecular hydrogen-bonding OH group band (6,600-7,100 cm(-1)). Large reduction of the intermolecular hydrogen-bonding band intensity at temperatures above the glass transition (T(g)) of the individual solids should explain the higher molecular mobility and lower viscosity in the rubber state. Mixing of the polyols with a high T(g) saccharide (maltose) or an inorganic salt (sodium tetraborate) shifted both the glass transition and the inflection point of the hydrogen-bonding band intensity to higher temperatures. The implications of these results for pharmaceutical formulation design and process monitoring (PAT) are discussed.

Observation of paramorphic phenomenon and non-tilted orthogonal smectic phases in hydrogen bonded ferroelectric liquid crystals for photonic applications

NASA Astrophysics Data System (ADS)

Subhasri, P.; Venugopal, D.; Jayaprakasam, R.; Chitravel, T.; Vijayakumar, V. N.

2018-06-01

A new class of hydrogen bonded ferroelectric liquid crystals (HBFLC) have been designed and synthesized by intermolecular hydrogen bonds between mesogenic 4-decyloxybenzoic acid (10OBA) and non-mesogenic (R)-(+)-Methylsuccinic acid (MSA) which have been confirmed through experimental and theoretical studies. Further, Mulliken population analysis clearly reveals that the existence of hydrogen bonds, strength and dynamic properties. Textural observation and its corresponding enthalpy values are analyzed by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) respectively. Paramorphic changes in Sm C* phase due to the change of refractive index, which clearly reveal that the complex could be used for filtering action in photonic devices. The transition from lone pair to π* with large stabilization energy evidently exposes the chiral phases in the present HBFLC complex. Intermolecular interaction is analyzed by using natural bond orbital (NBO) studies. The highest energy in the HOMO-LUMO shows the stable phase in the HBFLC complex. Molecular structure of the HBFLC complex possesses the monoclinic which has been evinced through x-ray analysis. The randomly oriented bunch of homogeneous molecules in Sm A* phase of the HBFLC complex is reported.

Influence of Different Etching Modes on Bond Strength to Enamel using Universal Adhesive Systems.

PubMed

Diniz, Ana Cs; Bandeca, Matheus C; Pinheiro, Larissa M; Dos Santosh Almeida, Lauber J; Torres, Carlos Rg; Borges, Alvaro H; Pinto, Shelon Cs; Tonetto, Mateus R; De Jesus Tavarez, Rudys R; Firoozmand, Leily M

2016-10-01

The adhesive systems and the techniques currently used are designed to provide a more effective adhesion with reduction of the protocol application. The objective of this study was to evaluate the bond strength of universal adhesive systems on enamel in different etching modes (self-etch and total etch). The mesial and distal halves of 52 bovine incisors, healthy, freshly extracted, were used and divided into seven experimental groups (n = 13). The enamel was treated in accordance with the following experimental conditions: FUE-Universal System - Futurabond U (VOCO) with etching; FUWE - Futurabond U (VOCO) without etching; SB-Total Etch System - Single Bond 2 (3M); SBUE-Universal System - Single Bond Universal (3M ESPE) with etching; SBUWE - Single Bond Universal (3M ESPE) without etching; CLE-Self-etch System - Clearfil SE Bond (Kuraray) was applied with etching; CLWE - Clearfil SE Bond (Kuraray) without etching. The specimens were made using the composite spectrum TPH (Dentsply) and stored in distilled water (37 ± 1°C) for 1 month. The microshear test was performed using the universal testing machine EMIC DL 2000 with the crosshead speed of 0.5 mm/minute. The bond strength values were analyzed using statistical tests (Kruskal-Wallis test and Mann-Whitney test) with Bonferroni correction. There was no statistically significant difference between groups (p < 0.05), where FUE (36.83 ± 4.9 MPa) showed the highest bond strength values and SBUWE (18.40 ± 2.2 MPa) showed the lowest bond strength values. The analysis of adhesive interface revealed that most failures occurred between the interface composite resin and adhesive. The universal adhesive system used in dental enamel varies according to the trademark, and the previous enamel etching for universal systems and the self-etch both induced greater bond strength values. Selective enamel etching prior to the application of a universal adhesive system is a relevant strategy for better performance bonding.

Bonding strategies for MIH-affected enamel and dentin.

PubMed

Krämer, Norbert; Bui Khac, Ngoc-Han Nana; Lücker, Susanne; Stachniss, Vitus; Frankenberger, Roland

2018-02-01

Aim of the present study was to evaluate resin composite adhesion to dental hard tissues affected by molar incisor hypomineralisation (MIH). 94 freshly extracted human molars and incisors (53 suffering MIH) were used. 68 teeth (35 with MIH) were used for μ-TBS tests in enamel and dentin, 26 (18 with MIH) for qualitative evaluation. Specimens were bonded with Clearfil SE Bond, Scotchbond Universal, and OptiBond FL. For MIH affected enamel, additional OptiBond FL groups with NaOCl and NaOCl+Icon were investigated. Beside fractographic analysis, also qualitative evaluations were performed using SEM at different magnifications as well as histological sectioning. Highest μ-TBS values were recorded with dentin specimens (ANOVA, mod. LSD, p<0.05). Results were independent of adhesive and dentin substrate (p>0.05). Pre-test failures did not occur in dentin specimens. Sound enamel specimens exhibited significantly higher μ-TBS values than MIH enamel (p<0.05). The two-step self-etch adhesive (Clearfil SE Bond) and the two-step etch-and-rinse adhesive (Scotchbond Universal) showed the lowest values in affected enamel specimens (p<0.05) with most pre-test failures (p<0.05). OptiBond FL on affected enamel showed better results than Clearfil SE Bond (p<0.05). An additional pre-treatment of affected enamel with NaOCl or NaOCl and Icon did not enhance enamel bonding (p>0.05), however, it caused less pre-test failures (p<0.05). Micromorphological analyses revealed that conventional phosphoric acid etching produces a much less pronounced etching pattern in affected enamel and a porous structure as weak link for the resin-enamel bond was identified. Bonding to porous hypomineralized MIH enamel is the limiting factor in adhesion to MIH teeth. MIH-affected dentin may be bonded conventionally. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Interest Rates and Coupon Bonds in Quantum Finance

NASA Astrophysics Data System (ADS)

Baaquie, Belal E.

2009-09-01

1. Synopsis; 2. Interest rates and coupon bonds; 3. Options and option theory; 4. Interest rate and coupon bond options; 5. Quantum field theory of bond forward interest rates; 6. Libor Market Model of interest rates; 7. Empirical analysis of forward interest rates; 8. Libor Market Model of interest rate options; 9. Numeraires for bond forward interest rates; 10. Empirical analysis of interest rate caps; 11. Coupon bond European and Asian options; 12. Empirical analysis of interest rate swaptions; 13. Correlation of coupon bond options; 14. Hedging interest rate options; 15. Interest rate Hamiltonian and option theory; 16. American options for coupon bonds and interest rates; 17. Hamiltonian derivation of coupon bond options; Appendixes; Glossaries; List of symbols; Reference; Index.

Influence of Bond Coat on HVOF-Sprayed Gradient Cermet Coating on Copper Alloy

NASA Astrophysics Data System (ADS)

Ke, Peng; Cai, Fei; Chen, Wanglin; Wang, Shuoyu; Ni, Zhenhang; Hu, Xiaohong; Li, Mingxi; Zhu, Guanghong; Zhang, Shihong

2017-06-01

Coatings are required on mold copper plates to prolong their service life through enhanced hardness, wear resistance, and oxidation resistance. In the present study, NiCr-30 wt.%Cr3C2 ceramic-metallic (cermet) layers were deposited by high velocity oxy-fuel (HVOF) spraying on different designed bond layers, including electroplated Ni, HVOF-sprayed NiCr, and double-decker Ni-NiCr. Annealing was also conducted on the gradient coating (GC) with NiCr bond layer to improve the wear resistance and adhesion strength. Coating microstructure was investigated by scanning electron microscopy and x-ray diffraction analysis. Mechanical properties including microhardness, wear resistance, and adhesion strength of the different coatings were evaluated systematically. The results show that the types of metallic bond layer and annealing process had a significant impact on the mechanical properties of the GCs. The GCs with electroplated Ni bond layer exhibited the highest adhesion strength (about 70 MPa). However, the GC with HVOF-sprayed NiCr bond layer exhibited better wear resistance. The wear resistance and adhesion strength of the coating with NiCr metallic bond layer were enhanced after annealing.

A single Watson-Crick G x C base pair in water: aqueous hydrogen bonds in hydrophobic cavities.

PubMed

Sawada, Tomohisa; Fujita, Makoto

2010-05-26

Hydrogen bond (H-bond) formation in water has been a challenging task because water molecules are constant competitors. In biological systems, however, stable H-bonds are formed by shielding the H-bonding sites from the competing water molecules within hydrophobic pockets. Inspired by the nature's elaborated way, we found that even mononucleotides (G and C) can form the minimal G x C Watson-Crick pair in water by simply providing a synthetic cavity that efficiently shields the Watson-Crick H-bonding sites. The minimal Watson-Crick structure in water was elucidated by NMR study and firmly characterized by crystallographic analysis. The crystal structure also displays that, within the cavity, coencapsulated anions and solvents efficiently mediate the minimal G x C Watson-Crick pair formation. Furthermore, the competition experiments with the other nucleobases clearly revealed the evident selectivity for the G x C base pairing in water. These results show the fact that a H-bonded nucleobase pair was effectively induced and stabilized in the local environment of an artificial hydrophobic cavity.

Toward the Prediction of Water Exchange Rates in Magnetic Resonance Imaging Contrast Agents: A Density Functional Theory Study.

PubMed

Regueiro-Figueroa, Martín; Platas-Iglesias, Carlos

2015-06-18

We present a theoretical investigation of Gd-Owater bonds in different complexes relevant as contrast agents in magnetic resonance imaging (MRI). The analysis of the Ln-Owater distances, electron density (ρBCP), and electron localization function (ELF) at the bond critical points of [Ln(DOTA)(H2O)](-) and [Ln(DTPA-BMA)(H2O)] indicates that the strength of the Ln-Owater bonds follows the order DTPA-BMA > DOTA (M isomer) > DOTA (m isomer). The ELF values decrease along the 4f period as the Ln-Owater bonds get shorter, in line with the labile capping bond phenomenon. Extension of these calculations to other Gd(3+) complexes allowed us to correlate the experimentally observed water exchange rates and the calculated ρBCP and ELF values. The water exchange reaction becomes faster as the Gd-Owater bonds are weakened, which is reflected in longer bond distances and lower values of ρBCP and ELF. DKH2 calculations show that the two coordinated water molecules may also have significantly different (17)O hyperfine coupling constants (HFCCs).

Microshear bond strength of composite resins to enamel and porcelain substrates utilizing unfilled versus filled resins.

PubMed

Najafi-Abrandabadi, Ahmad; Najafi-Abrandabadi, Siamak; Ghasemi, Amir; Kotick, Philip G

2014-11-01

Failures such as marginal discoloration and composite chipping are still the problems of tooth-colored restorations on the substrate of enamel and porcelain, which some of these problems are consequently as a result of failures in the bonding layer. Using filled resin has been recently introduced to increase the bond strength of this layer. The aim of this study was to compare the microshear bond strength (μ-SBS) of composite resins to enamel incubated in periods of 24 h and 9 months and porcelain with unfilled resin and flowable composites (filled resin). In this in vitro study, two groups of 75 enamel samples with different storage times (24 h and 9 months) and a group of 75 porcelain samples were used. They were divided into 5 experimental groups of 15 samples in each. Composite cylinders in tygon tubes were bonded on the surface of acid-etched enamel and pretreated porcelain. Wave, Wave MV, Wave HV, Grandioflow and Margin Bond were used as bonding agents. The μ-SBS was measured at the speed of 1.0 mm/min. The bond strengths were analyzed with one-way analysis of variance (ANOVA) test followed by Tukey test. P < 0.05 was selected as the level of statistical significance in this study. The results showed that for enamel (24 h), the μ-SBS of the Wave MV and Wave HV groups were significantly lower than the Margin Bond group. Tukey test indicated the absence of a significant difference between the μ-SBS of the Wave group and the Margin Bond group. However, the μ-SBS of the Grandioflow group was significantly higher than the one for the Margin Bond as a bonding agent. In enamel (9 months), there was a significant difference between the Grandioflow and Margin Bond groups. Regarding bonding to the porcelain the one-way ANOVA test did not show a significant difference among the groups. This study revealed that flowable composites (filled resins) can be used instead of unfilled resins in bonding composite resins to enamel and porcelain substrates.

Nicotinamidase/pyrazinamidase of Mycobacterium tuberculosis forms homo-dimers stabilized by disulfide bonds

PubMed Central

Rueda, Daniel; Sheen, Patricia; Gilman, Robert H.; Bueno, Carlos; Santos, Marco; Pando-Robles, Victoria; Batista, Cesar V.; Zimic, Mirko

2014-01-01

Recombinant wild-pyrazinamidase from H37Rv M. tuberculosis was analyzed by gel electrophoresis under differential reducing conditions to evaluate its quaternary structure. PZAse was fractionated by size exclusion chromatography under non-reducing conditions. PZAse activity was measured and mass spectrometry analysis was performed to determine the identity of proteins by de novo sequencing and to determine the presence of disulfide bonds. This study confirmed that M. tuberculosis wild type PZAse was able to form homo-dimers in vitro. Homo-dimers showed a slightly lower specific PZAse activity compared to monomeric PZAse. PZAse dimers were dissociated into monomers in response to reducing conditions. Mass spectrometry analysis confirmed the existence of disulfide bonds (C72-C138 and C138-C138) stabilizing the quaternary structure of the PZAse homo-dimer. PMID:25199451

Application of argon atmospheric cold plasma for indium tin oxide (ITO) based diodes

NASA Astrophysics Data System (ADS)

Akbari Nia, S.; Jalili, Y. Seyed; Salar Elahi, A.

2017-09-01

Transparent Conductive Oxide (TCO) layers due to transparency, high conductivity and hole injection capability have attracted a lot of attention. One of these layers is Indium Tin Oxide (ITO). ITO due to low resistance, transparency in the visible spectrum and its proper work function is widely used in the manufacture of organic light emitting diodes and solar cells. One way for improving the ITO surface is plasma treatment. In this paper, changes in surface morphology, by applying argon atmospheric pressure cold plasma, was studied through Atomic Force Microscopic (AFM) image analysis and Fourier Transform Infrared Spectroscopy (FTIR) analysis. FTIR analysis showed functional groups were not added or removed, but chemical bond angle and bonds strength on the surface were changed and also AFM images showed that surface roughness was increased. These factors lead to the production of diodes with enhanced Ohmic contact and injection mechanism which are more appropriate in industrial applications.

Hydration dynamics of a lipid membrane: Hydrogen bond networks and lipid-lipid associations

NASA Astrophysics Data System (ADS)

Srivastava, Abhinav; Debnath, Ananya

2018-03-01

Dynamics of hydration layers of a dimyristoylphosphatidylcholine (DMPC) bilayer are investigated using an all atom molecular dynamics simulation. Based upon the geometric criteria, continuously residing interface water molecules which form hydrogen bonds solely among themselves and then concertedly hydrogen bonded to carbonyl, phosphate, and glycerol head groups of DMPC are identified. The interface water hydrogen bonded to lipids shows slower relaxation rates for translational and rotational dynamics compared to that of the bulk water and is found to follow sub-diffusive and non-diffusive behaviors, respectively. The mean square displacements and the reorientational auto-correlation functions are slowest for the interfacial waters hydrogen bonded to the carbonyl oxygen since these are buried deep in the hydrophobic core among all interfacial water studied. The intermittent hydrogen bond auto-correlation functions are calculated, which allows breaking and reformations of the hydrogen bonds. The auto-correlation functions for interfacial hydrogen bonded networks develop humps during a transition from cage-like motion to eventual power law behavior of t-3/2. The asymptotic t-3/2 behavior indicates translational diffusion dictated dynamics during hydrogen bond breaking and formation irrespective of the nature of the chemical confinement. Employing reactive flux correlation analysis, the forward rate constant of hydrogen bond breaking and formation is calculated which is used to obtain Gibbs energy of activation of the hydrogen bond breaking. The relaxation rates of the networks buried in the hydrophobic core are slower than the networks near the lipid-water interface which is again slower than bulk due to the higher Gibbs energy of activation. Since hydrogen bond breakage follows a translational diffusion dictated mechanism, chemically confined hydrogen bond networks need an activation energy to diffuse through water depleted hydrophobic environments. Our calculations reveal that the slow relaxation rates of interfacial waters in the vicinity of lipids are originated from the chemical confinement of concerted hydrogen bond networks. The analysis suggests that the networks in the hydration layer of membranes dynamically facilitate the water mediated lipid-lipid associations which can provide insights on the thermodynamic stability of soft interfaces relevant to biological systems in the future.

Nature and kinetic analysis of carbon-carbon bond fragmentation reactions of cation radicals derived from SET-oxidation of lignin model compounds.

PubMed

Cho, Dae Won; Parthasarathi, Ramakrishnan; Pimentel, Adam S; Maestas, Gabriel D; Park, Hea Jung; Yoon, Ung Chan; Dunaway-Mariano, Debra; Gnanakaran, S; Langan, Paul; Mariano, Patrick S

2010-10-01

Features of the oxidative cleavage reactions of diastereomers of dimeric lignin model compounds, which are models of the major types of structural units found in the lignin backbone, were examined. Cation radicals of these substances were generated by using SET-sensitized photochemical and Ce(IV) and lignin peroxidase promoted oxidative processes, and the nature and kinetics of their C-C bond cleavage reactions were determined. The results show that significant differences exist between the rates of cation radical C1-C2 bond cleavage reactions of 1,2-diaryl-(β-1) and 1-aryl-2-aryloxy-(β-O-4) propan-1,3-diol structural units found in lignins. Specifically, under all conditions C1-C2 bond cleavage reactions of cation radicals of the β-1 models take place more rapidly than those of the β-O-4 counterparts. The results of DFT calculations on cation radicals of the model compounds show that the C1-C2 bond dissociation energies of the β-1 lignin model compounds are significantly lower than those of the β-O-4 models, providing clear evidence for the source of the rate differences.

The integrity of bonded amalgam restorations: a clinical evaluation after five years.

PubMed

Mach, Zbynek; Regent, Jan; Staninec, Michal; Mrklas, Lubor; Setcos, James C

2002-04-01

Bonded amalgam restorations have been studied extensively in vitro, but few long term clinical studies exist. The authors examined the clinical performance of bonded amalgam restorations after five years of clinical service an compared it with that of nonbonded amalgam restorations. The authors placed 75 bonded and 62 nonbonded amalgam restorations in patients needing restorations. Most of the restorations were placed in conventional preparations; six bonded restorations were placed in nonretentive cavities. They were evaluated after a five-year period of clinical service by two trained dentists using a mirror and explorer and following modified U.S. Public Health Service criteria. Statistical analysis (via Fisher exact test) showed no significant differences between the two techniques when conventional preparations were used. Restorations in nonretentive preparations were successful during this period. Bonded and nonbonded amalgam restorations yielded similar results in conventional preparations after five years of clinical service. Bonded amalgam restorations were clinically successful in a limited number of nonretentive preparations over a five-year period. Bonded amalgam restorations can be used successfully in conventional preparations and possibly in nonretentive preparations as well, and can be expected to last at least five years.

Origins of Protons in C-H Bond Insertion Products of Phenols: Proton-Self-Sufficient Function via Water Molecules.

PubMed

Luo, Zhoujie; Gao, Ya; Zhu, Tong; Zhang, John Zenghui; Xia, Fei

2017-08-31

Water molecules can serve as proton shuttles for proton transfer in the C-H bond insertion reactions catalyzed by transition metal complexes. Recently, the control experiments performed for C-H bond insertion of phenol and anisol by gold carbenes show that large discrepancy exists in the yields of hydrogenated and deuterated products. Thus, we conducted a detailed theoretical analysis on the function of water molecules in the C-H bond insertion reactions. The comparison of calculated results and control experiments indicates that the solution water molecules play a crucial role of proton shuttle in C-H bond insertion. In particular, it was found that the hydroxyl groups in phenols were capable of donating protons via water shuttles for the production of C-H products, which had a substantial influence on the yields of inserted products. The hydroxyl groups instead of C-H bonds in phenols function like "proton reservoirs" in the C-H bond insertion, which we call the "proton self-sufficient" (PSS) function of phenol. The PSS function of phenol indicates that the substrates with and without proton reservoirs will lead to different C-H bond insertion products.

Structure and Bonding analysis of the cationic electrophilic phosphinidene complexes of iron, ruthenium, and osmium [(η(5)-C5Me5)(CO)2M{PN(i)Pr2}]+, [(η(5)-C5H5)(CO)2M{PNR2}]+ (R = Me, (i)Pr), and [(η(5)-C5H5)(PMe3)2M{PNMe2}]+ (M = Fe, Ru, Os).

PubMed

Pandey, Krishna K; Tiwari, Pradeep; Patidar, Pankaj

2012-11-29

Quantum-chemical DFT calculations for the electronic, molecular structure and M-PNR(2) bonding analyses of the experimentally known cationic electrophilic phosphinidene complexes [(η(5)-C(5)Me(5))(CO)(2)M{PN(i)Pr(2)}](+) and of the model complexes [(η(5)-C(5)H(5))(CO)(2)M{PNR(2)}](+) (R = (i)Pr, Me) and [(η(5)-C(5)H(5))(PMe(3))(2)M{PNMe(2)}](+) were carried out using BP86/TZ2P/ZORA level of theory. The calculated geometrical parameters of the studied complexes are in good agreement with the reported experimental values. The short M-P bond distances and calculated Pauling bond orders (range of 1.23-1.68), suggest the presence of M-P multiple bond characters. The Hirshfeld charge analysis shows that the overall charge flows from phosphinidene ligand to metal fragment. The M-P σ-bonding orbitals are well-occupied (>1.80e). The energy decomposition analysis revealed that the contribution of the electrostatic interaction ΔE(elstat) is, in all studied complexes, significantly larger (55.2-62.6%) than the orbital interactions ΔE(orb). The orbital interactions between metal and PNR(2) in [(η(5)-C(5)H(5))(L)(2)M{PNR(2)}](+) arise mainly from M ← PNR(2) σ-donation. The π-bonding contribution (19-36%) is much smaller than the σ-bonding. The interaction energies, as well as bond dissociation energies, depend on the auxiliary ligand framework around the metal and decrease in the order (η(5)-C(5)H(5)) > (η(5)-C(5)Me(5)) and CO > PMe(3). Upon substitution of R = (i)Pr with smaller group R = Me, the M-PNR(2) bond strength slightly decreases.

SEM/XPS analysis of fractured adhesively bonded graphite fibre surface resin-rich/graphite fibre composites

NASA Technical Reports Server (NTRS)

Devilbiss, T. A.; Wightman, J. P.; Progar, D. J.

1988-01-01

Samples of graphite fiber-reinforced polyimide were fabricated allowing the resin to accumulate at the composite surface. These surface resin-rich composites were then bonded together and tested for lap shear strength both before and after thermal aging. Lap shear strength did not appear to show a significant improvement over that previously recorded for resin-poor samples and was shown to decrease with increasing aging time and temperature.

Hydrothermal synthesis and characterization of a novel supramolecular network compound of Co(NIA) 2(H 2O) 4 with molecular ladder hydrogen bond chains (NIA=nicotinate)

NASA Astrophysics Data System (ADS)

Jia, Hong-Bin; Yu, Jie-Hui; Xu, Ji-Qing; Ye, Ling; Ding, Hong; Jing, Wei-Jie; Wang, Tie-Gang; Xu, Jia-Ning; Li, Zeng-Chun

2002-10-01

By hydrothermal method, a novel supramolecular compound, Co(NIA) 2(H 2O) 4 was synthesized and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffractometer, indicating that it is a novel polyporous supramolecule with molecular ladder hydrogen-bonded chains. TGA curve shows its thermal stability up to 520 °C.

Quantum entanglement and quantum information in biological systems (DNA)

NASA Astrophysics Data System (ADS)

Hubač, Ivan; Švec, Miloslav; Wilson, Stephen

2017-12-01

Recent studies of DNA show that the hydrogen bonds between given base pairs can be treated as diabatic systems with spin-orbit coupling. For solid state systems strong diabaticity and spin-orbit coupling the possibility of forming Majorana fermions has been discussed. We analyze the hydrogen bonds in the base pairs in DNA from this perspective. Our analysis is based on a quasiparticle supersymmetric transformation which couples electronic and vibrational motion and includes normal coordinates and the corresponding momenta. We define qubits formed by Majorana fermions in the hydrogen bonds and also discuss the entangled states in base pairs. Quantum information and quantum entropy are introduced. In addition to the well-known classical information connected with the DNA base pairs, we also consider quantum information and show that the classical and quantum information are closely connected.

Recent mass spectrometry-based techniques and considerations for disulfide bond characterization in proteins.

PubMed

Lakbub, Jude C; Shipman, Joshua T; Desaire, Heather

2018-04-01

Disulfide bonds are important structural moieties of proteins: they ensure proper folding, provide stability, and ensure proper function. With the increasing use of proteins for biotherapeutics, particularly monoclonal antibodies, which are highly disulfide bonded, it is now important to confirm the correct disulfide bond connectivity and to verify the presence, or absence, of disulfide bond variants in the protein therapeutics. These studies help to ensure safety and efficacy. Hence, disulfide bonds are among the critical quality attributes of proteins that have to be monitored closely during the development of biotherapeutics. However, disulfide bond analysis is challenging because of the complexity of the biomolecules. Mass spectrometry (MS) has been the go-to analytical tool for the characterization of such complex biomolecules, and several methods have been reported to meet the challenging task of mapping disulfide bonds in proteins. In this review, we describe the relevant, recent MS-based techniques and provide important considerations needed for efficient disulfide bond analysis in proteins. The review focuses on methods for proper sample preparation, fragmentation techniques for disulfide bond analysis, recent disulfide bond mapping methods based on the fragmentation techniques, and automated algorithms designed for rapid analysis of disulfide bonds from liquid chromatography-MS/MS data. Researchers involved in method development for protein characterization can use the information herein to facilitate development of new MS-based methods for protein disulfide bond analysis. In addition, individuals characterizing biotherapeutics, especially by disulfide bond mapping in antibodies, can use this review to choose the best strategies for disulfide bond assignment of their biologic products. Graphical Abstract This review, describing characterization methods for disulfide bonds in proteins, focuses on three critical components: sample preparation, mass spectrometry data, and software tools.

A theoretical investigation into the strength of N-NO2 bonds, ring strain and electrostatic potential upon formation of intermolecular H-bonds between HF and the nitro group in nitrogen heterocyclic rings C n H2n N-NO2 (n = 2-5), RDX and HMX.

PubMed

Wang, Bao-Guo; Ren, Fu-de; Shi, Wen-Jing

2015-11-01

Changes in N-NO2 bond strength, ring strain energy and electrostatic potential upon formation of intermolecular H-bonds between HF and the nitro group in nitrogen heterocyclic rings C n H2n N-NO2 (n = 2-5), RDX and HMX were investigated using DFT-B3LYP and MP2(full) methods with the 6-311++G(2df,2p) and aug-cc-pVTZ basis sets. Analysis of electron density shifts was also carried out. The results indicate that H-bonding energy correlates well with the increment of ring strain energy. Upon complex formation, the strength of the N-NO2 trigger-bond is enhanced, suggesting reduced sensitivity, while judged by the increased ring strain energy, sensitivity is increased. However, some features of the molecular surface electrostatic potential, such as a local maximum above the N-NO2 bond and ring, σ + (2) and electrostatic balance parameter ν, remain essentially unchanged upon complex formation, and only a small change in the impact sensitivity h 50 is suggested. It is not sufficient to determine sensitivity solely on the basis of trigger bond or ring strain; as a global feature of a molecule, the molecular surface electrostatic potential is available to help judge the change of sensitivity in H-bonded complexes. Graphical Abstract The strengthened N-NO2 bond suggests reduced sensitivity, while it is reverse by theincreased ring strain energy upon the complex formation. However, the molecular surfaceelectrostatic potential (V S) shows the little change of h 50. The V S should be taken into accountin the analysis of explosive sensitivity in the H-bonded complex.

Molecular structure and vibrational spectra of three substituted 4-thioflavones by density functional theory and ab initio Hartree-Fock calculations

NASA Astrophysics Data System (ADS)

Li, Xiao-Hong; Liu, Xiang-Ru; Zhang, Xian-Zhou

2011-01-01

The vibrational frequencies of three substituted 4-thioflavones in the ground state have been calculated using the Hartree-Fock and density functional method (B3LYP) with 6-31G* and 6-31+G** basis sets. The structural analysis shows that there exists H-bonding in the selected compounds and the hydrogen bond lengths increase with the augment of the conjugate parameters of the substituent group on the benzene ring. A complete vibrational assignment aided by the theoretical harmonic wavenumber analysis was proposed. The theoretical spectrograms for FT-IR spectra of the title compounds have been constructed. In addition, it is noted that the selected compounds show significant activity against Shigella flexniri. Several electronic properties and thermodynamic parameters were also calculated.

Maxima of |Ψ|2: a connection between quantum mechanics and Lewis structures.

PubMed

Lüchow, Arne

2014-04-30

The maxima of squared electronic wave functions |Ψ|2 are analyzed for a number of small molecules. They are in principle observables and show considerable chemical insight from first principles. The maxima contain substantial information about the relative electron positions in a molecule, such as the pairing of opposite spin electrons and the Pauli repulsion which are lost in the electron density. Single bond and double bond as well as polar bond pairs and lone pairs are obtained from the maximum analysis. In many cases, we find a correspondence to the electron arrangements in molecules as assumed by Lewis in 1916. Copyright © 2014 Wiley Periodicals, Inc.

Sol-gel dip coating of yttria-stabilized tetragonal zirconia dental ceramic by aluminosilicate nanocomposite as a novel technique to improve the bonding of veneering porcelain.

PubMed

Madani, Azamsadat; Nakhaei, Mohammadreza; Karami, Parisa; Rajabzadeh, Ghadir; Salehi, Sahar; Bagheri, Hossein

2016-01-01

The aim of this in vitro study was to evaluate the effect of silica and aluminosilicate nanocomposite coating of zirconia-based dental ceramic by a sol-gel dip-coating technique on the bond strength of veneering porcelain to the yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) in vitro. Thirty Y-TZP blocks (10 mm ×10 mm ×3 mm) were prepared and were assigned to four experimental groups (n=10/group): C, without any further surface treatment as the control group; S, sandblasted using 110 μm alumina powder; Si, silica sol dip coating + calcination; and Si/Al, aluminosilicate sol dip coating + calcination. After preparing Y-TZP samples, a 3 mm thick layer of the recommended porcelain was fired on the coated Y-TZP surface. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray analysis were used to characterize the coating and the nature of the bonding between the coating and zirconia. To examine the zirconia-porcelain bond strength, a microtensile bond strength (μTBS) approach was chosen. FT-IR study showed the formation of silica and aluminosilicate materials. XRD pattern showed the formation of new phases consisting of Si, Al, and Zr in coated samples. SEM showed the formation of a uniform coating on Y-TZP samples. Maximum μTBS values were obtained in aluminosilicate samples, which were significantly increased compared to control and sandblasted groups (P=0.013 and P<0.001, respectively). This study showed that aluminosilicate sol-gel dip coating can be considered as a convenient, less expensive reliable method for improving the bond strength between dental Y-TZP ceramics and veneering porcelain.

Sol–gel dip coating of yttria-stabilized tetragonal zirconia dental ceramic by aluminosilicate nanocomposite as a novel technique to improve the bonding of veneering porcelain

PubMed Central

Madani, Azamsadat; Nakhaei, Mohammadreza; Karami, Parisa; Rajabzadeh, Ghadir; Salehi, Sahar; Bagheri, Hossein

2016-01-01

The aim of this in vitro study was to evaluate the effect of silica and aluminosilicate nanocomposite coating of zirconia-based dental ceramic by a sol–gel dip-coating technique on the bond strength of veneering porcelain to the yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) in vitro. Thirty Y-TZP blocks (10 mm ×10 mm ×3 mm) were prepared and were assigned to four experimental groups (n=10/group): C, without any further surface treatment as the control group; S, sandblasted using 110 μm alumina powder; Si, silica sol dip coating + calcination; and Si/Al, aluminosilicate sol dip coating + calcination. After preparing Y-TZP samples, a 3 mm thick layer of the recommended porcelain was fired on the coated Y-TZP surface. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray analysis were used to characterize the coating and the nature of the bonding between the coating and zirconia. To examine the zirconia–porcelain bond strength, a microtensile bond strength (μTBS) approach was chosen. FT-IR study showed the formation of silica and aluminosilicate materials. XRD pattern showed the formation of new phases consisting of Si, Al, and Zr in coated samples. SEM showed the formation of a uniform coating on Y-TZP samples. Maximum μTBS values were obtained in aluminosilicate samples, which were significantly increased compared to control and sandblasted groups (P=0.013 and P<0.001, respectively). This study showed that aluminosilicate sol–gel dip coating can be considered as a convenient, less expensive reliable method for improving the bond strength between dental Y-TZP ceramics and veneering porcelain. PMID:27478376

Moisture effect on interfacial integrity of epoxy-bonded system: a hierarchical approach

NASA Astrophysics Data System (ADS)

Tam, Lik-ho; Lun Chow, Cheuk; Lau, Denvid

2018-01-01

The epoxy-bonded system has been widely used in various applications across different scale lengths. Prior investigations have indicated that the moisture-affected interfacial debonding is the major failure mode of such a system, but the fundamental mechanism remains unknown, such as the basis for the invasion of water molecules in the cross-linked epoxy and the epoxy-bonded interface. This prevents us from predicting the long-term performance of the epoxy-related applications under the effect of the moisture. Here, we use full atomistic models to investigate the response of the epoxy-bonded system towards the adhesion test, and provide a detailed analysis of the interfacial integrity under the moisture effect and the associated debonding mechanism. Molecular dynamics simulations show that water molecules affect the hierarchical structure of the epoxy-bonded system at the nanoscale by disrupting the film-substrate interaction and the molecular interaction within the epoxy, which leads to the detachment of the epoxy thin film, and the final interfacial debonding. The simulation results show good agreement with the experimental results of the epoxy-bonded system. Through identifying the relationship between the epoxy structure and the debonding mechanism at multiple scales, it is shown that the hierarchical structure of the epoxy-bonded system is crucial for the interfacial integrity. In particular, the available space of the epoxy-bonded system, which consists of various sizes ranging from the atomistic scale to the macroscale and is close to the interface facilitates the moisture accumulation, leading to a distinct interfacial debonding when compared to the dry scenario.

Low temperature X-ray structure analyses combined with NBO studies of a new heteroleptic octa-coordinated Holmium(III) complex with N,N,N-tridentate hydrazono-phthalazine-type ligand

NASA Astrophysics Data System (ADS)

Soliman, Saied M.; El-Faham, Ayman

2018-04-01

The new heteroleptic [HoL(H2O)5]Br3 complex, L is hydrazono-phthalazine ligand, is synthesized and its molecular structure aspects were analyzed using single crystal X-ray structure (SCXRD), Hirshfeld (HF) analysis, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) method. The SCXRD showed that the Ho is octa-coordinated with one N,N,N-tridentate ligand L and five water molecules. The HF analysis is used to analyze the molecular packing in the [HoL(H2O)5]Br3crystal structure. The complex cations are connected via strong Osbnd H⋯Br and Nsbnd H⋯Br H-bonding interactions which have greater importance than the Csbnd H⋯Br contacts. Also, all the Hosbnd N and Hosbnd O bonds have the characteristics of closed shell interactions using QTAIM. The natural orbitals included in these interactions were analyzed using NBO method. The alpha LP*(8)Ho and beta LP*(4)Ho which have mainly s-orbital characters are the most important anti-bonding natural orbitals included in all Ho-N and Hosbnd O bonds. The rest of the Ho anti-bonding orbitals which have either p or d-orbital characters shared partially in the Ho-ligands interactions. Natural charges analysis revealed the presence of significant amount of electron density (0.9225-0.9300 e) transferred from the ligands to Ho (2.0700-2.0775 e). Spherical spin density with ∼4.0 e is predicted over the Ho atom.

The significance of nanoparticles on bond strength of polymer concrete to steel

DOE PAGES

Douba, A.; Genedy, M.; Matteo, E. N.; ...

2017-01-03

Here, polymer concrete (PC) is a commonly used material in construction due to its improved durability and good bond strength to steel substrate. PC has been suggested as a repair and seal material to restore the bond between the cement annulus and the steel casing in wells that penetrate formations under consideration for CO 2 sequestration. Nanoparticles including Multi-Walled Carbon Nano Tubes (MWCNTs), Aluminum Nanoparticles (ANPs) and Silica Nano particles (SNPs) were added to an epoxy-based PC to examine how the nanoparticles affect the bond strength of PC to a steel substrate. Slant shear tests were used to determine themore » bond strength of PC incorporating nanomaterials to steel; results reveal that PC incorporating nanomaterials has an improved bond strength to steel substrate compared with neat PC. In particular, ANPs improve the bond strength by 51% over neat PC. Local shear stresses, extracted from Finite Element (FE) analysis of the slant shear test, were found to be as much as twice the apparent/average shear/bond strength. These results suggest that the impact of nanomaterials is higher than that shown by the apparent strength. Fourier Transform Infrared (FTIR) measurements of epoxy with and without nanomaterials showed ANPs to influence curing of epoxy, which might explain the improved bond strength of PC incorporating ANPs.« less

The significance of nanoparticles on bond strength of polymer concrete to steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Douba, A.; Genedy, M.; Matteo, E. N.

Here, polymer concrete (PC) is a commonly used material in construction due to its improved durability and good bond strength to steel substrate. PC has been suggested as a repair and seal material to restore the bond between the cement annulus and the steel casing in wells that penetrate formations under consideration for CO 2 sequestration. Nanoparticles including Multi-Walled Carbon Nano Tubes (MWCNTs), Aluminum Nanoparticles (ANPs) and Silica Nano particles (SNPs) were added to an epoxy-based PC to examine how the nanoparticles affect the bond strength of PC to a steel substrate. Slant shear tests were used to determine themore » bond strength of PC incorporating nanomaterials to steel; results reveal that PC incorporating nanomaterials has an improved bond strength to steel substrate compared with neat PC. In particular, ANPs improve the bond strength by 51% over neat PC. Local shear stresses, extracted from Finite Element (FE) analysis of the slant shear test, were found to be as much as twice the apparent/average shear/bond strength. These results suggest that the impact of nanomaterials is higher than that shown by the apparent strength. Fourier Transform Infrared (FTIR) measurements of epoxy with and without nanomaterials showed ANPs to influence curing of epoxy, which might explain the improved bond strength of PC incorporating ANPs.« less

Design/Analysis of the JWST ISIM Bonded Joints for Survivability at Cryogenic Temperatures

NASA Technical Reports Server (NTRS)

Bartoszyk, Andrew; Johnston, John; Kaprielian, Charles; Kuhn, Jonathan; Kunt, Cengiz; Rodini, Benjamin; Young, Daniel

2005-01-01

Contents include the following: JWST/ISIM introduction. Design and analysis challenges for ISIM bonded joints. JWST/ISIM joint designs. Bonded joint analysis. Finite element modeling. Failure criteria and margin calculation. Analysis/test correlation procedure. Example of test data and analysis.

Disulfide bonding arrangements in active forms of the somatomedin B domain of human vitronectin.

PubMed

Kamikubo, Yuichi; De Guzman, Roberto; Kroon, Gerard; Curriden, Scott; Neels, Jaap G; Churchill, Michael J; Dawson, Philip; Ołdziej, Stanisław; Jagielska, Anna; Scheraga, Harold A; Loskutoff, David J; Dyson, H Jane

2004-06-01

The N-terminal cysteine-rich somatomedin B (SMB) domain (residues 1-44) of the human glycoprotein vitronectin contains the high-affinity binding sites for plasminogen activator inhibitor-1 (PAI-1) and the urokinase receptor (uPAR). We previously showed that the eight cysteine residues of recombinant SMB (rSMB) are organized into four disulfide bonds in a linear uncrossed pattern (Cys(5)-Cys(9), Cys(19)-Cys(21), Cys(25)-Cys(31), and Cys(32)-Cys(39)). In the present study, we use an alternative method to show that this disulfide bond arrangement remains a major preferred one in solution, and we determine the solution structure of the domain using NMR analysis. The solution structure shows that the four disulfide bonds are tightly packed in the center of the domain, replacing the traditional hydrophobic core expected for a globular protein. The few noncysteine hydrophobic side chains form a cluster on the outside of the domain, providing a distinctive binding surface for the physiological partners PAI-1 and uPAR. The hydrophobic surface consists mainly of side chains from the loop formed by the Cys(25)-Cys(31) disulfide bond, and is surrounded by conserved acidic and basic side chains, which are likely to contribute to the specificity of the intermolecular interactions of this domain. Interestingly, the overall fold of the molecule is compatible with several arrangements of the disulfide bonds. A number of different disulfide bond arrangements were able to satisfy the NMR restraints, and an extensive series of conformational energy calculations performed in explicit solvent confirmed that several disulfide bond arrangements have comparable stabilization energies. An experimental demonstration of the presence of alternative disulfide conformations in active rSMB is provided by the behavior of a mutant in which Asn(14) is replaced by Met. This mutant has the same PAI-1 binding activity as rVN1-51, but its fragmentation pattern following cyanogen bromide treatment is incompatible with the linear uncrossed disulfide arrangement. These results suggest that active forms of the SMB domain may have a number of allowed disulfide bond arrangements as long as the Cys(25)-Cys(31) disulfide bond is preserved.

Vibrational spectral investigation and natural bond orbital analysis of pharmaceutical compound 7-Amino-2,4-dimethylquinolinium formate - DFT approach.

PubMed

Suresh, D M; Amalanathan, M; Sebastian, S; Sajan, D; Hubert Joe, I; Bena Jothy, V; Nemec, Ivan

2013-11-01

The molecular geometry, the normal mode frequencies and corresponding vibrational assignments, natural bond orbital analysis and the HOMO-LUMO analysis of 7-Amino-2,4-dimethylquinolinium formate in the ground state were performed by B3LYP levels of theory using the 6-31G(d) basis set. The optimised bond lengths and bond angles are in good agreement with the X-ray data. The vibrational spectra of the title compound which is calculated by DFT method, reproduces vibrational wave numbers and intensities with an accuracy which allows reliable vibrational assignments. The possibility of N-H⋯O hydrogen bonding was identified using NBO analysis. Natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

The determinants of bond angle variability in protein/peptide backbones: A comprehensive statistical/quantum mechanics analysis.

PubMed

Improta, Roberto; Vitagliano, Luigi; Esposito, Luciana

2015-11-01

The elucidation of the mutual influence between peptide bond geometry and local conformation has important implications for protein structure refinement, validation, and prediction. To gain insights into the structural determinants and the energetic contributions associated with protein/peptide backbone plasticity, we here report an extensive analysis of the variability of the peptide bond angles by combining statistical analyses of protein structures and quantum mechanics calculations on small model peptide systems. Our analyses demonstrate that all the backbone bond angles strongly depend on the peptide conformation and unveil the existence of regular trends as function of ψ and/or φ. The excellent agreement of the quantum mechanics calculations with the statistical surveys of protein structures validates the computational scheme here employed and demonstrates that the valence geometry of protein/peptide backbone is primarily dictated by local interactions. Notably, for the first time we show that the position of the H(α) hydrogen atom, which is an important parameter in NMR structural studies, is also dependent on the local conformation. Most of the trends observed may be satisfactorily explained by invoking steric repulsive interactions; in some specific cases the valence bond variability is also influenced by hydrogen-bond like interactions. Moreover, we can provide a reliable estimate of the energies involved in the interplay between geometry and conformations. © 2015 Wiley Periodicals, Inc.

Evaluation of enamel damages following orthodontic bracket debonding in fluorosed teeth bonded with adhesion promoter.

PubMed

Baherimoghadam, Tahreh; Akbarian, Sahar; Rasouli, Reza; Naseri, Navid

2016-01-01

To evaluate shear bond strength (SBS) of the orthodontic brackets bonded to fluorosed and nonfluorosed teeth using Light Bond with and without adhesion promoters and compare their enamel damages following debonding. In this study, 30 fluorosed (Thylstrup and Fejerskov Index = 4-5) and 30 nonfluorosed teeth were randomly distributed between two subgroups according to the bonding materials: Group 1, fluorosed teeth bonded with Light Bond; Group 2, fluorosed teeth bonded with adhesion promoters and Light Bond; Group 3, nonfluorosed teeth bonded with Light Bond; Group 4, nonfluorosed bonded with adhesion promoters and Light Bond. After bonding, the SBS of the brackets was tested with a universal testing machine. Stereomicroscopic evaluation was performed by unbiased stereology in all teeth to determine the amount of adhesive remnants and the number and length of enamel cracks before bonding and after debonding. The data were analyzed using two-way analysis of variance, Kruskal-Wallis, Wilcoxon Signed Rank, and Mann-Whitney test. While fluorosis reduced the SBS of orthodontic bracket (P = 0.017), Enhance Locus Ceruleus LC significantly increased the SBS of the orthodontic bracket in fluorosed and nonfluorosed teeth (P = 0.039). Significant increasing in the number and length of enamel crack after debonding was found in all four groups. There were no significant differences in the length of enamel crack increased after debonding among four groups (P = 0.768) while increasing in the number of enamel cracks after debonding was significantly different among the four groups (P = 0.023). Teeth in Group 2 showed the highest enamel damages among four groups following debonding. Adhesion promoters could improve the bond strength of orthodontic brackets, but conservative debonding methods for decreasing enamel damages would be necessary.

Mean bond-length variations in crystals for ions bonded to oxygen

PubMed Central

2017-01-01

Variations in mean bond length are examined in oxide and oxysalt crystals for 55 cation configurations bonded to O2−. Stepwise multiple regression analysis shows that mean bond length is correlated to bond-length distortion in 42 ion configurations at the 95% confidence level, with a mean coefficient of determination (〈R 2〉) of 0.35. Previously published correlations between mean bond length and mean coordination number of the bonded anions are found not to be of general applicability to inorganic oxide and oxysalt structures. For two of 11 ions tested for the 95% confidence level, mean bond lengths predicted using a fixed radius for O2− are significantly more accurate as those predicted using an O2− radius dependent on coordination number, and are statistically identical otherwise. As a result, the currently accepted ionic radii for O2− in different coordinations are not justified by experimental data. Previously reported correlation between mean bond length and the mean electronegativity of the cations bonded to the oxygen atoms of the coordination polyhedron is shown to be statistically insignificant; similar results are obtained with regard to ionization energy. It is shown that a priori bond lengths calculated for many ion configurations in a single structure-type leads to a high correlation between a priori and observed mean bond lengths, but a priori bond lengths calculated for a single ion configuration in many different structure-types leads to negligible correlation between a priori and observed mean bond lengths. This indicates that structure type has a major effect on mean bond length, the magnitude of which goes beyond that of the other variables analyzed here.

Shear bond strength of one-step self-etch adhesives: pH influence

PubMed Central

Poggio, Claudio; Beltrami, Riccardo; Scribante, Andrea; Colombo, Marco; Chiesa, Marco

2015-01-01

Background: The aim of this study was to compare the shear bond strength of four one-step self-etch adhesives with different pH values to enamel and dentin. Materials and Methods: In this in vitro study, 200 bovine permanent mandibular incisors were used. Four one-step self-etch adhesives with different pH values were tested both on enamel and on dentin: Adper™ Easy Bond Self-Etch Adhesive (pH = 0.8-1), Futurabond NR (pH=2), G-aenial Bond (pH = 1.5), Clearfil S3 Bond (pH = 2.7). After adhesive systems application, a nanohybrid composite resin was inserted into the bonded surface. The specimens were placed in a universal testing machine. The shear bond strength was performed at a cross-head speed of 1 mm/min until the sample rupture. The shear bond strength values (MPa) of the different groups were compared with analysis of variance after that Kolmogorov and Smirnov tests were applied to assess normality of distributions. P < 0.05 was considered as significant. Results: In enamel shear bond strength, the highest shear bond strength values were reported with Futurabond NR (P < 0.01); however, no significant differences were found with Clearfil S3 Bond. The others adhesive systems showed lower shear bond strength values with significant differences between them (P < 0.05). When comparing the dentin shear bond strength, the lowest shear bond strength values were reported with Clearfil S3 Bond (P < 0.05), while there were no significant differences among the other three products (P > 0.05). Conclusion: The pH values of adhesive systems did not influence significantly their shear bond strength to enamel or dentin. PMID:26005459

Assessment of Proper Bonding Methods and Mechanical Characterization FPGA CQFPs

NASA Technical Reports Server (NTRS)

Davis, Milton C.

2008-01-01

This presentation discusses fractured leads on field-programmable gate array (FPGA) during flight vibration. Actions taken to determine root cause and resolution of the failure include finite element analysis (FEA) and vibration testing and scanning electron microscopy (with X-ray microanalysis) and energy dispersive spectrometry (SEM/EDS) failure assessment. Bonding methods for surface mount parts is assessed, including critical analysis and assessment of random fatigue damage. Regarding ceramic quad flat pack (CQFP) lead fracture, after disassembling the attitude control electronics (ACE) configuration, photographs showed six leads cracked on FPGA RTSX72SU-1 CQ208B package located on the RWIC card. An identical package (FPGA RTSX32SU-1 CQ208B) mounted on the RWIC did not results in cracked pins due to vibration. FPGA lead failure theories include workmanship issues in the lead-forming, material defect in the leads of the FPGA packages, and the insecure mounting of the board in the card guides, among other theories. Studies were conducted using simple calculations to determine the response and fatigue life of the package. Shorter packages exhibited more response when loaded by out-of-plane displacement of PCB while taller packages exhibit more response when loaded by in-plane acceleration of PCB. Additionally, under-fill did not contribute to reducing stress in leads due to out-of-plane PCB loading or from component twisting, as much as corner bonding. The combination of corner bond and under-fill is best to address mechanical and thermal S/C environment. Test results of bonded parts showed reduced (dampened) amplitude and slightly shifted peaks at the un-bonded natural frequency and an additional response at the bonded frequency. Stress due to PCBB out-of-plane loading was decreased on in the corners when only a corner bond was used. Future work may address CQFP fatigue assessment, including the investigation of discrepancy in predicted fatigue damage, as well as comparing fatigue life and fatigue damage cycle ration computed using FEA and Miner's rule to results from a fatigue assessment software program.

Microstructural evolution and micromechanical properties of gamma-irradiated Au ball bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yusoff, Wan Yusmawati Wan, E-mail: yusmawati@upnm.edu.my; Ismail, Roslina, E-mail: roslina.ismail@ukm.my; Jalar, Azman, E-mail: azmn@ukm.my

2014-07-01

The effect of gamma radiation on the mechanical and structural properties of gold ball bonds was investigated. Gold wires from thermosonic wire bonding were exposed to gamma rays from a Cobalt-60 source at a low dose (5 Gy). The load–depth curve of nanoindentation for the irradiated gold wire bond has an apparent staircase shape during loading compared to the as-received sample. The hardness of the specimens calculated from the nanoindentation shows an increase in value from 0.91 to 1.09 GPa for specimens after exposure. The reduced elastic modulus for irradiated specimens significantly increased as well, with values from 75.18 tomore » 98.55 GPa. The change in intrinsic properties due to gamma radiation was investigated using dual-focused ion beam and high-resolution transmission electron microscope analysis. The dual-focused ion beam and high-resolution transmission electron microscope images confirmed the changes in grain structure and the presence of dislocations. The scanning electron microscope micrographs of focused ion beam cross sections showed that the grain structure of the gold became elongated and smaller after exposure to gamma rays. Meanwhile, high-resolution transmission electron microscopy provided evidence that gamma radiation induced dislocation of the atomic arrangement. - Highlights: • Nanoindentation technique provides a detailed characterisation of Au ball bond. • P–h curve of irradiated Au ball bond shows an apparent pop-in event. • Hardness and reduced modulus increased after exposure. • Elongated and smaller grain structure in irradiated specimens • Prevalent presence of dislocations in the atomic arrangement.« less

Thermal Strain Analysis of Optic Fiber Sensors

PubMed Central

Her, Shiuh-Chuan; Huang, Chih-Ying

2013-01-01

An optical fiber sensor surface bonded onto a host structure and subjected to a temperature change is analytically studied in this work. The analysis is developed in order to assess the thermal behavior of an optical fiber sensor designed for measuring the strain in the host structure. For a surface bonded optical fiber sensor, the measuring sensitivity is strongly dependent on the bonding characteristics which include the protective coating, adhesive layer and the bonding length. Thermal stresses can be generated due to a mismatch of thermal expansion coefficients between the optical fiber and host structure. The optical fiber thermal strain induced by the host structure is transferred via the adhesive layer and protective coating. In this investigation, an analytical expression of the thermal strain and stress in the optical fiber is presented. The theoretical predictions are validated using the finite element method. Numerical results show that the thermal strain and stress are linearly dependent on the difference in thermal expansion coefficients between the optical fiber and host structure and independent of the thermal expansion coefficients of the adhesive and coating. PMID:23385407

Global disulfide bond profiling for crude snake venom using dimethyl labeling coupled with mass spectrometry and RADAR algorithm.

PubMed

Huang, Sheng Yu; Chen, Sung Fang; Chen, Chun Hao; Huang, Hsuan Wei; Wu, Wen Guey; Sung, Wang Chou

2014-09-02

Snake venom consists of toxin proteins with multiple disulfide linkages to generate unique structures and biological functions. Determination of these cysteine connections usually requires the purification of each protein followed by structural analysis. In this study, dimethyl labeling coupled with LC-MS/MS and RADAR algorithm was developed to identify the disulfide bonds in crude snake venom. Without any protein separation, the disulfide linkages of several cytotoxins and PLA2 could be solved, including more than 20 disulfide bonds. The results show that this method is capable of analyzing protein mixture. In addition, the approach was also used to compare native cytotoxin 3 (CTX III) and its scrambled isomer, another category of protein mixture, for unknown disulfide bonds. Two disulfide-linked peptides were observed in the native CTX III, and 10 in its scrambled form, X-CTX III. This is the first study that reports a platform for the global cysteine connection analysis on a protein mixture. The proposed method is simple and automatic, offering an efficient tool for structural and functional studies of venom proteins.

Fluorine analysis of human dentin surrounding resin composite after fluoride application by μ-PIGE/PIXE analysis

NASA Astrophysics Data System (ADS)

Okuyama, Katsushi; Komatsu, Hisanori; Yamamoto, Hiroko; Pereira, Patricia N. R.; Bedran-Russo, Ana K.; Nomachi, Masaharu; Sato, Takahiro; Sano, Hidehiko

2011-10-01

The use of fluoride for the prevention of caries is based on the transformation of hydroxylapatite to fluoroapatite in the presence of fluoride ions, thereby strengthening tooth structure. Adhesion of dentin and resin composite (tooth-colored restoration material) requires a dentin bonding system, since resin composite is not able to adhere to dentin directly. Demineralization of dentin by acid etching is an important step in the dentin bonding system, however, demineralization also introduces weaknesses in tooth structure. If the demineralized dentin could be strengthened by the application of fluoride, then the dentin-resin composite bond strength might also improve. To test this hypothesis, the present study evaluated the influence of fluoride applications on the strength of the dentin-resin composite bond by (1) tensile strength testing analyses, (2) SEM analyses of tooth structure, and (3) detection of calcium (Ca) and fluorine (F) distribution patterns by micro proton-induced X-ray emission (μ-PIXE) and micro proton-induced gamma-ray emission (μ-PIGE) analyses conducted at the Takasaki Ion Accelerators for Advanced Radiation Application (TIARA) at the Takasaki Advanced Radiation Research Institute (TARRI). In this study, the dentin in extracted human molars was exposed by grinding and the dentin was etched with 35% phosphoric acid. Fluoride was applied at two concentrations, 0.022% (100 ppm F) and 2.21% (10,000 ppm F) NaF solution, for two time periods, 30 and 60 s, prior to bonding the resin composite with the treated dentin. Controls were prepared in the same manner, but without the fluoride application. Bond strength was measured with a micro-tensile testing unit, and the fluorine and calcium distributions at the interface between dentin and resin composite were detected by μ-PIGE and μ-PIXE analysis, respectively. Results indicate that the 10,000 ppm F applications resulted in higher bond strengths than observed in either the 100 ppm F applications or the control group. In addition, PIGE analyses showed high concentrations of fluorine in the hybrid bonding layer of the 10,000 ppm F samples, suggesting that the fluorine contributes to the strength of the dentin-resin composite bond. Detection of fluoroapatite within the hybrid bonding layer suggests that bond strength involves remineralization processes.

Transition-state charge transfer reveals electrophilic, ambiphilic, and nucleophilic carbon-hydrogen bond activation.

PubMed

Ess, Daniel H; Nielsen, Robert J; Goddard, William A; Periana, Roy A

2009-08-26

Absolutely localized molecular orbital energy decomposition analysis of C-H activation transition states (TSs), including Pt, Au, Ir, Ru, W, Sc, and Re metal centers, shows an electrophilic, ambiphilic, and nucleophilic charge transfer (CT) continuum irrespective of the bonding paradigm (oxidative addition, sigma-bond metathesis, oxidative hydrogen migration, 1,2-substitution). Pt(II) insertion and Au(III) substitution TSs are highly electrophilic and dominated by C-H bond to metal/ligand orbital stabilization, while Ir-X and Ru-X (X = R, NH(2), OR, or BOR(2)) substitution TSs are ambiphilic in nature. In this ambiphilic activation regime, an increase in one direction of CT typically leads to a decrease in the reverse direction. Comparison of Tp(CO)Ru-OH and Tp(CO)Ru-NH(2) complexes showed no evidence for the classic d(pi)-p(pi) repulsion model. Complexes such as and Cp(CO)(2)W-B(OR)(2), (PNP)Ir(I), Cp(2)ScMe, and (acac-kappaO,kappaO)(2)Re(III)-OH were found to mediate nucleophilic C-H activation, where the CT is dominated by the metal/ligand orbital to C-H antibonding orbital interaction. This CT continuum ultimately affects the metal-alkyl intermediate polarization and possible functionalization reactions. This analysis will impact the design of new activation reactions and stimulate the discovery of more nucleophilic activation complexes.

Molecular reorganization of selected quinoline derivatives in the ground and excited states—Investigations via static DFT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Błaziak, Kacper; Panek, Jarosław J.; Jezierska, Aneta, E-mail: aneta.jezierska@chem.uni.wroc.pl

2015-07-21

Quinoline derivatives are interesting objects to study internal reorganizations due to the observed excited-state-induced intramolecular proton transfer (ESIPT). Here, we report on computations for selected 12 quinoline derivatives possessing three kinds of intramolecular hydrogen bonds. Density functional theory was employed for the current investigations. The metric and electronic structure simulations were performed for the ground state and first excited singlet and triplet states. The computed potential energy profiles do not show a spontaneous proton transfer in the ground state, whereas excited states exhibit this phenomenon. Atoms in Molecules (AIM) theory was applied to study the nature of hydrogen bonding, whereasmore » Harmonic Oscillator Model of aromaticity index (HOMA) provided data of aromaticity evolution as a derivative of the bridge proton position. The AIM-based topological analysis confirmed the presence of the intramolecular hydrogen bonding. In addition, using the theory, we were able to provide a quantitative illustration of bonding transformation: from covalent to the hydrogen. On the basis of HOMA analysis, we showed that the aromaticity of both rings is dependent on the location of the bridge proton. Further, the computed results were compared with experimental data available. Finally, ESIPT occurrence was compared for the three investigated kinds of hydrogen bridges, and competition between two bridges in one molecule was studied.« less

Vibrational spectroscopic and non-linear optical activity studies on nicotinanilide : A DFT approach

NASA Astrophysics Data System (ADS)

Premkumar, S.; Jawahar, A.; Mathavan, T.; Dhas, M. Kumara; Benial, A. Milton Franklin

2015-06-01

The molecular structure of nicotinanilide was optimized by the DFT/B3LYP method with cc-pVTZ basis set using Gaussian 09 program. The first order hyperpolarizability of the molecule was calculated, which exhibits the higher nonlinear optical activity. The natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction, which leads to the higher nonlinear optical activity of the molecule. The Frontier molecular orbitals analysis of the molecule shows that the delocalization of electron density occurs within the molecule. The lower energy gap indicates that the hydrogen bond formation between the charged species. The vibrational frequencies were calculated and assigned on the basis of potential energy distribution calculation using the VEDA 4.0 program and the corresponding vibrational spectra were simulated. Hence, the nicotinanilide molecule can be a good candidate for second-order NLO material.

Evaluation of experimental coating to improve the zirconia-veneering ceramic bond strength.

PubMed

Matani, Jay D; Kheur, Mohit; Jambhekar, Shantanu Subhashchandra; Bhargava, Parag; Londhe, Aditya

2014-12-01

To evaluate the shear bond strength (SBS) between zirconia and veneering ceramic following different surface treatments of zirconia. The efficacy of an experimental zirconia coating to improve the bond strength was also evaluated. Zirconia strips were fabricated and were divided into four groups as per their surface treatment: polished (control), airborne-particle abrasion, laser irradiation, and application of the experimental coating. The surface roughness and the residual monoclinic content were evaluated before and after the respective surface treatments. A scanning electron microscope (SEM) analysis of the experimental surfaces was performed. All specimens were subjected to shear force in a universal testing machine. The SBS values were analyzed with one-way ANOVA followed by Bonferroni post hoc for groupwise comparisons. The fractured specimens were examined to observe the failure mode. The SBS (29.17 MPa) and roughness values (0.80) of the experimental coating group were the highest among the groups. The residual monoclinic content was minimal (0.32) when compared to the remaining test groups. SEM analysis revealed a homogenous surface well adhered to an undamaged zirconia base. The other test groups showed destruction of the zirconia surface. The analysis of failure following bond strength testing showed entirely cohesive failures in the veneering ceramic in all study groups. The experimental zirconia surface coating is a simple technique to increase the microroughness of the zirconia surface, and thereby improve the SBS to the veneering ceramic. It results in the least monoclinic content and produces no structural damage to the zirconia substructure. © 2014 by the American College of Prosthodontists.

Molecular structure, vibrational spectroscopic (FT-IR, FT-Raman), UV-vis spectra, first order hyperpolarizability, NBO analysis, HOMO and LUMO analysis, thermodynamic properties of benzophenone 2,4-dicarboxylic acid by ab initio HF and density functional method

NASA Astrophysics Data System (ADS)

Chaitanya, K.

2012-02-01

The FT-IR (4000-450 cm -1) and FT-Raman spectra (3500-100 cm -1) of benzophenone 2,4-dicarboxylic acid (2,4-BDA) have been recorded in the condensed state. Density functional theory calculation with B3LYP/6-31G(d,p) basis set have been used to determine ground state molecular geometries (bond lengths and bond angles), harmonic vibrational frequencies, infrared intensities, Raman activities and bonding features of the title compounds. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The first order hyperpolarizability ( β0) and related properties ( β, α0 and Δ α) of 2,4-BDA is calculated using HF/6-31G(d,p) method on the finite-field approach. The stability of molecule has been analyzed by using NBO analysis. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics. The calculated HOMO and LUMO energies show that charge transfer occurs within these molecules. Mulliken population analysis on atomic charges is also calculated. Because of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated. Finally, the UV-vis spectra and electronic absorption properties were explained and illustrated from the frontier molecular orbitals.

NMR analysis of cleaved Escherichia coli thioredoxin (1-73/74-108) and its P76A variant: cis/trans peptide isomerization.

PubMed Central

Yu, W. F.; Tung, C. S.; Wang, H.; Tasayco, M. L.

2000-01-01

Inspection of high resolution three-dimensional (3D) structures from the protein database reveals an increasing number of cis-Xaa-Pro and cis-Xaa-Yaa peptide bonds. However, we are still far from being able to predict whether these bonds will remain cis upon single-site substitution of Pro or Yaa and/or cleavage of a peptide bond close to it in the sequence. We have chosen oxidized Escherichia coli thioredoxin (Trx), a member of the Trx superfamily with a single alpha/beta domain and cis P76 to determine the effect of single-site substitution and/or cleavage on this isomer. Standard two-dimensional (2D) NMR analysis were performed on cleaved Trx (1-73/74-108) and its P76A variant. Analysis of the NOE connectivities indicates remarkable similarity between the secondary and supersecondary structure of the noncovalent complexes and Trx. Analysis of the 2D version of the HCCH-TOCSY and HMQC-NOESY-HMQC and 13C-filtered HMQC-NOESY spectra of cleaved Trx with uniformly 13C-labeled 175 and P76 shows surprising conservation of both cis P76 and packing of 175 against W31. A similar NMR analysis of its P76A variant provides no evidence for cis A76 and shows only subtle local changes in both the packing of 175 and the interstrand connectivities between its most protected hydrophobic strands (beta2 and beta4). Indeed, a molecular simulation model for the trans P76A variant of Trx shows only subtle local changes around the substitution site. In conclusion, cleavage of R73 is insufficient to provoke cis/trans isomerization of P76, but cleavage and single-site substitution (P76A) favors the trans isomer. PMID:10739243

Ethers on Si(001): A Prime Example for the Common Ground between Surface Science and Molecular Organic Chemistry.

PubMed

Pecher, Lisa; Laref, Slimane; Raupach, Marc; Tonner, Ralf

2017-11-20

By using computational chemistry it has been shown that the adsorption of ether molecules on Si(001) under ultrahigh vacuum conditions can be understood with classical concepts of organic chemistry. Detailed analysis of the two-step reaction mechanism-1) formation of a dative bond between the ether oxygen atom and a Lewis acidic surface atom and 2) nucleophilic attack of a nearby Lewis basic surface atom-shows that it mirrors acid-catalyzed ether cleavage in solution. The O-Si dative bond is the strongest of its kind, and the reactivity in step 2 defies the Bell-Evans-Polanyi principle. Electron rearrangement during C-O bond cleavage has been visualized with a newly developed method for analyzing bonding, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular S N 2 reactions. Our findings illustrate how surface science and molecular chemistry can mutually benefit from each other and unexpected insight can be gained. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lumpkin, Gregory R.; Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234; Pruneda, Miguel

2007-04-15

The radiation tolerance of synthetic pyrochlore and defect fluorite compounds has been studied using ion irradiation. We show that the results can be quantified in terms of the critical temperature for amorphization, structural parameters, classical Pauling electronegativity difference, and disorder energies. Our results demonstrate that radiation tolerance is correlated with a change in the structure from pyrochlore to defect fluorite, a smaller unit cell dimension, and lower cation-anion disorder energy. Radiation tolerance is promoted by an increase in the Pauling cation-anion electronegativity difference or, in other words, an increase in the ionicity of the chemical bonds. A further analysis ofmore » the data indicates that, of the two possible cation sites in ideal pyrochlore, the smaller B-site cation appears to play the major role in bonding. This result is supported by ab initio calculations of the structure and bonding, showing a correlation between the Mulliken overlap populations of the B-site cation and the critical temperature. - Graphical abstract: Three-dimensional representation of the predicted critical amorphization temperature in pyrochlores.« less

A comparison of retentive strength of implant cement depending on various methods of removing provisional cement from implant abutment

PubMed Central

Keum, Eun-Cheol

2013-01-01

PURPOSE This study evaluated the effectiveness of various methods for removing provisional cement from implant abutments, and what effect these methods have on the retention of prosthesis during the definitive cementation. MATERIALS AND METHODS Forty implant fixture analogues and abutments were embedded in resin blocks. Forty cast crowns were fabricated and divided into 4 groups each containing 10 implants. Group A was cemented directly with the definitive cement (Cem-Implant). The remainder were cemented with provisional cement (Temp-Bond NE), and classified according to the method for cleaning the abutments. Group B used a plastic curette and wet gauze, Group C used a rubber cup and pumice, and Group D used an airborne particle abrasion technique. The abutments were observed using a stereomicroscope after removing the provisional cement. The tensile bond strength was measured after the definitive cementation. Statistical analysis was performed using one-way analysis of variance test (α=.05). RESULTS Group B clearly showed provisional cement remaining, whereas the other groups showed almost no cement. Groups A and B showed a relatively smooth surface. More roughness was observed in Group C, and apparent roughness was noted in Group D. The tensile bond strength tests revealed Group D to have significantly the highest tensile bond strength followed in order by Groups C, A and B. CONCLUSION A plastic curette and wet gauze alone cannot effectively remove the residual provisional cement on the abutment. The definitive retention increased when the abutments were treated with rubber cup/pumice or airborne particle abraded to remove the provisional cement. PMID:24049563

Effects of surface treatment and artificial aging on the shear bond strength of orthodontic brackets bonded to four different provisional restorations.

PubMed

Al Jabbari, Youssef S; Al Taweel, Sara M; Al Rifaiy, Mohammed; Alqahtani, Mohammed Q; Koutsoukis, Theodoros; Zinelis, Spiros

2014-07-01

To evaluate the combined effects of material type, surface treatment, and thermocycling on the bond strength of orthodontic brackets to materials used for the fabrication of provisional crowns. Four materials were included in this study (ProTemp, Trim Plus, Trim II, and Superpont C+B). Sixty cylindrical specimens (1 × 3 cm) were prepared from each material and equally divided into three groups. The first group was ground with silica carbide paper, the second was polished with pumice, and the last group was sandblasted with 50-µm aluminum oxide particles. Stainless-steel maxillary central incisor brackets (Victory Series, 3M) were bonded to the provisional material specimens with Transbond XT light-cured composite resin, and half of the specimens from each group were thermocycled 500 times in 5°C and 55°C water baths. Then the brackets were debonded with shear testing, and the results were statistically analyzed by three-way analysis of variance and Tukey's multiple-comparison tests at α  =  0.05. Adhesive Remnant Index (ARI) was also identified. Before and after thermocycling, ProTemp materials showed the highest shear bond strength with orthodontic brackets (10.3 and 13.1 MPa, respectively). The statistical analysis indicated an interaction among the three independent variables (P < .05) and statistically significant differences in bond strength among provisional materials (P < .001), surface treatments (P < .001), and thermocycling (P < .05). According to the ARI, most groups demonstrated adhesive failure. The provisional material type, surface treatment, and artificial aging have a significant effect on bond strength. Sandblasting treatment exerts a beneficial effect on shear bond strength.

Energetic Analysis of Conjugated Hydrocarbons Using the Interacting Quantum Atoms Method.

PubMed

Jara-Cortés, Jesús; Hernández-Trujillo, Jesús

2018-07-05

A number of aromatic, antiaromatic, and nonaromatic organic molecules was analyzed in terms of the contributions to the electronic energy defined in the quantum theory of atoms in molecules and the interacting quantum atoms method. Regularities were found in the exchange and electrostatic interatomic energies showing trends that are closely related to those of the delocalization indices defined in the theory. In particular, the CC interaction energies between bonded atoms allow to rationalize the energetic stabilization associated with the bond length alternation in conjugated polyenes. This approach also provides support to Clar's sextet rules devised for aromatic systems. In addition, the H⋯H bonding found in some of the aromatic molecules studied was of an attractive nature, according to the stabilizing exchange interaction between the bonded H atoms. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [ Co ( terpy ) 2 ] 2 +

DOE PAGES

Biasin, Elisa; van Driel, Tim Brandt; Kjær, Kasper S.; ...

2016-06-30

Here, we study the structural dynamics of photoexcited [Co(terpy) 2] 2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of themore » high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~7 ps.« less

Disulfide Bond Formation and Activation of Escherichia coli β-Galactosidase under Oxidizing Conditions

PubMed Central

Seras-Franzoso, Joaquin; Affentranger, Roman; Ferrer-Navarro, Mario; Daura, Xavier; Villaverde, Antonio

2012-01-01

Escherichia coli β-galactosidase is probably the most widely used reporter enzyme in molecular biology, cell biology, and biotechnology because of the easy detection of its activity. Its large size and tetrameric structure make this bacterial protein an interesting model for crystallographic studies and atomic mapping. In the present study, we investigate a version of Escherichia coli β-galactosidase produced under oxidizing conditions, in the cytoplasm of an Origami strain. Our data prove the activation of this microbial enzyme under oxidizing conditions and clearly show the occurrence of a disulfide bond in the β-galactosidase structure. Additionally, the formation of this disulfide bond is supported by the analysis of a homology model of the protein that indicates that two cysteines located in the vicinity of the catalytic center are sufficiently close for disulfide bond formation. PMID:22286993

The role of the [CpM(CO)2](-) chromophore in the optical properties of the [Cp2ThMCp(CO)2](+) complexes, where M = Fe, Ru and Os. A theoretical view.

PubMed

Cantero-López, Plinio; Le Bras, Laura; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

2015-12-14

The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2](+) complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2](-) chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

Wafer-Level Hermetic Package by Low-Temperature Cu/Sn TLP Bonding with Optimized Sn Thickness

NASA Astrophysics Data System (ADS)

Wu, Zijian; Cai, Jian; Wang, Qian; Wang, Junqiang; Wang, Dejun

2017-10-01

In this paper, a wafer-level package with hermetic sealing by low-temperature Cu/Sn transient liquid phase (TLP) bonding for a micro-electromechanical system was introduced. A Cu bump with a Sn cap and sealing ring were fabricated simultaneously by electroplating. The model of Cu/Sn TLP bonding was established and the thicknesses of Cu and Sn were optimized after a series of bonding experiments. Cu/Sn wafer-level bonding was undertaken at 260°C for 30 min under a vacuum condition. An average shear strength of 50.36 MPa and a fine leak rate of 1.9 × 10-8 atm cc/s were achieved. Scanning electron microscope photos of the Cu/Sn/Cu interlayers were presented, and energy dispersive x-ray analysis was conducted simultaneously. The results showed that the Sn was completely consumed to form the stable intermetallic compound Cu3Sn. An aging test of 200 h at 200°C was conducted to test the performance of the hermetic sealing, while the results of shear strength, fine leak rate and bonding interface were also set out.

Structural, bonding, and electronic properties of the hexagonal ferroelectric and paraelectric phases of LuMnO{sub 3} compound: A density functional theory study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sousa, A. M.; Coutinho, W. S.; Lima, A. F.

2015-02-21

We have investigated the structural, bonding, and electronic properties of both ferroelectric (FE) and paraelectric (PE) phases of the hexagonal LuMnO{sub 3} compound using calculations based on density functional theory. The structural properties have been determined by employing the generalized gradient approximation with Perdew-Burke-Ernzerhof and Wu-Cohen parameterization. The bonding and electronic properties have been treated by recently developed modified Becke-Johnson exchange potential, which succeeded to open a band gap for both PE and FE phases, in agreement with experimental predictions. The Bader’s topological analysis of electronic density showed that the character of the Lu–O axial bonds changes when the crystalmore » exhibits the PE → FE structural transition. This fact is in agreement with experimental findings. The covalent character of the Lu–O bond significantly increases due to orbital hybridization between the Lu 5d{sub z}{sup 2} and O 2p{sub z}-states. This bonding mechanism causes the ferroelectricity in the hexagonal LuMnO{sub 3} compound.« less

Interfacial structure, bonding and composition of InAs and GaSb thin films determined using coherent Bragg rod analysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cionca, C.; Walko, D. A.; Yacoby, Y.

2007-01-01

We have used Bragg rod x-ray diffraction combined with a direct method of phase retrieval to extract atomic resolution electron-density maps of a complementary series of heteroepitaxial III-V semiconductor samples. From the three-dimensional electron-density maps we derive the monolayer spacings, the chemical compositions, and the characteristics of the bonding for all atomic planes in the film and across the film-substrate interface. InAs films grown on GaSb(001) under two different As conditions (using dimer or tetramer forms) both showed conformal roughness and mixed GaAs/InSb interfacial bonding character. The As tetramer conditions favored InSb bonding at the interface while, in the casemore » of the dimer, the percentages corresponding to GaAs and InSb bonding were equal within the experimental error. The GaSb film grown on InAs(001) displayed significant In and As interdiffusion and had a relatively large fraction of GaAs-like bonds at the interface.« less

Effect of thione primers on adhesive bonding between an indirect composite material and Ag-Pd-Cu-Au alloy.

PubMed

Imai, Hideyuki; Koizumi, Hiroyasu; Shimoe, Saiji; Hirata, Isao; Matsumura, Hideo; Nikawa, Hiroki

2014-01-01

The current study evaluated the effect of primers on the shear bond strength of an indirect composite material joined to a silverpalladium-copper-gold (Ag-Pd-Cu-Au) alloy (Castwell). Disk specimens were cast from the alloy and were air-abraded with alumina. Eight metal primers were applied to the alloy surface. A light-polymerized indirect composite material (Solidex) was bonded to the alloy. Shear bond strength was determined both before and after the application of thermocycling. Two groups primed with Metaltite (thione) and M. L. Primer (sulfide) showed the greatest post-thermocycling bond strength (8.8 and 6.5 MPa). The results of the X-ray photoelectron spectroscopic (XPS) analysis suggested that the thione monomer (MTU-6) in the Metaltite primer was strongly adsorbed onto the Ag-Pd-Cu-Au alloy surface even after repeated cleaning with acetone. The application of either the thione (MTU-6) or sulfide primer is effective for enhancing the bonding between a composite material and Ag-Pd-Cu-Au alloy.

GDAP: a web tool for genome-wide protein disulfide bond prediction.

PubMed

O'Connor, Brian D; Yeates, Todd O

2004-07-01

The Genomic Disulfide Analysis Program (GDAP) provides web access to computationally predicted protein disulfide bonds for over one hundred microbial genomes, including both bacterial and achaeal species. In the GDAP process, sequences of unknown structure are mapped, when possible, to known homologous Protein Data Bank (PDB) structures, after which specific distance criteria are applied to predict disulfide bonds. GDAP also accepts user-supplied protein sequences and subsequently queries the PDB sequence database for the best matches, scans for possible disulfide bonds and returns the results to the client. These predictions are useful for a variety of applications and have previously been used to show a dramatic preference in certain thermophilic archaea and bacteria for disulfide bonds within intracellular proteins. Given the central role these stabilizing, covalent bonds play in such organisms, the predictions available from GDAP provide a rich data source for designing site-directed mutants with more stable thermal profiles. The GDAP web application is a gateway to this information and can be used to understand the role disulfide bonds play in protein stability both in these unusual organisms and in sequences of interest to the individual researcher. The prediction server can be accessed at http://www.doe-mbi.ucla.edu/Services/GDAP.

Preparation, structure and analysis of the bonding in the molecular entity (OSO)2Li{[AlF(ORF)3]Li[Al(ORF)4]} (RF = C(CF3)3).

PubMed

Cameron, T Stanley; Nikiforov, Grigory B; Passmore, Jack; Rautiainen, J Mikko

2010-03-14

The (SO(2))(2)Li[AlF(OR(F))(3)]Li[Al(OR(F))(4)] (1) (R(F) = C(CF(3))(3)) molecular entity was obtained by thermal decomposition of Li[Al(OR(F))(4)] followed by crystallization from liquid SO(2). 1, containing two SO(2) molecules eta(1)-O coordinated to Li(+), was structurally characterized by single crystal X-ray diffraction and NMR spectroscopy in SO(2)(l). Bonding analyses of 1 (bond valency units, AIM analysis, atomic charges, bond orders) show that 1 can be either considered as a Li(OSO)(2)(+) complex stabilized by the large WCA [AlF(OR(F))(3)](-)Li(+)[Al(OR(F))(4)](-) or as consisting of 2 SO(2), 2 Li(+), [AlF(OR(F))(3)](-), and [Al(OR(F))(4)](-) joined by electrostatic interactions into the discrete molecular entity 1. The bonding between Li(+) and SO(2) molecules is shown to be almost completely attributable to monopole-induced dipole electrostatic interactions. Theoretical gas phase lithium ion affinity of SO(2) is determined to be stronger than its silver(I) ion affinity owing largely to the shorter lithium SO(2) contacts in the calculated structures that increase the electrostatic interaction.

Hydrogen bonding interactions in PN...HX complexes: DFT and ab initio studies of structure, properties and topology.

PubMed

Varadwaj, Pradeep Risikrishna

2010-05-01

Spin-restricted DFT (X3LYP and B3LYP) and ab initio (MP2(fc) and CCSD(fc)) calculations in conjunction with the Aug-CC-pVDZ and Aug-CC-pVTZ basis sets were performed on a series of hydrogen bonded complexes PN...HX (X = F, Cl, Br) to examine the variations of their equilibrium gas phase structures, energetic stabilities, electronic properties, and vibrational characteristics in their electronic ground states. In all cases the complexes were predicted to be stable with respect to the constituent monomers. The interaction energy (Delta E) calculated using a super-molecular model is found to be in this order: PN...HF > PN...HCl > PN...HBr in the series examined. Analysis of various physically meaningful contributions arising from the Kitaura-Morokuma (KM) and reduced variational space self-consistent-field (RVS-SCF) energy decomposition procedures shows that the electrostatic energy has significant contribution to the over-all interaction energy. Dipole moment enhancement (Delta mu) was observed in these complexes expected of predominant dipole-dipole electrostatic interaction and was found to follow the trend PN...HF > PN...HCl > PN...HBr at the CCSD level. However, the DFT (X3LYP and B3LYP) and MP2 levels less accurately determined these values (in this order HF < HCl < HBr). Examination of the harmonic vibrational modes reveals that the PN and HX bands exhibit characteristic blue- and red shifts with concomitant bond contraction and elongation, respectively, on hydrogen bond formation. The topological or critical point (CP) analysis using the static quantum theory of atoms in molecules (QTAIM) of Bader was considered to classify and to gain further insight into the nature of interaction existing in the monomers PN and HX, and between them on H-bond formation. It is found from the analysis of the electron density rho ( c ), the Laplacian of electron charge density nabla(2)rho(c), and the total energy density (H ( c )) at the critical points between the interatomic regions that the interaction N...H is indeed electrostatic in origin (rho(c) > 0, nabla(2)rho(c) > 0 and H(c) > 0 at the BCP) whilst the bonds in PN (rho(c) > 0, nabla(2)rho(c) > 0 and H(c) < 0) and HX ((rho(c) > 0, nabla(2)rho(c) < 0 and H(c) < 0)) are predominantly covalent. A natural bond orbital (NBO) analysis of the second order perturbation energy lowering, E((2)), caused by charge transfer mechanism shows that the interaction N...H is n(N) --> BD*(HX) delocalization.

Orthodontic bracket bonding without previous adhesive priming: A meta-regression analysis.

PubMed

Altmann, Aline Segatto Pires; Degrazia, Felipe Weidenbach; Celeste, Roger Keller; Leitune, Vicente Castelo Branco; Samuel, Susana Maria Werner; Collares, Fabrício Mezzomo

2016-05-01

To determine the consensus among studies that adhesive resin application improves the bond strength of orthodontic brackets and the association of methodological variables on the influence of bond strength outcome. In vitro studies were selected to answer whether adhesive resin application increases the immediate shear bond strength of metal orthodontic brackets bonded with a photo-cured orthodontic adhesive. Studies included were those comparing a group having adhesive resin to a group without adhesive resin with the primary outcome measurement shear bond strength in MPa. A systematic electronic search was performed in PubMed and Scopus databases. Nine studies were included in the analysis. Based on the pooled data and due to a high heterogeneity among studies (I(2)  =  93.3), a meta-regression analysis was conducted. The analysis demonstrated that five experimental conditions explained 86.1% of heterogeneity and four of them had significantly affected in vitro shear bond testing. The shear bond strength of metal brackets was not significantly affected when bonded with adhesive resin, when compared to those without adhesive resin. The adhesive resin application can be set aside during metal bracket bonding to enamel regardless of the type of orthodontic adhesive used.

Characteristics of Amorphophallus campanulatus Modified Starch as Novel Adsorbent for Nickel and Cadmium Removal from Aqueous Solution

NASA Astrophysics Data System (ADS)

Lestari, A. Y. D.; Dewi, L. K.

2018-05-01

Novel adsorbents are succesfully manufactured from Amorphophalluscampanulatus (Porang or Suweg or Elephant Foot Yam or Foot Yam) starch. The experiment focused on modifiying the starch with citric acid and detailing those morphologies and chemical bonds. Analysis with FTIR and SEM showed that PTM (modified porous porang starch) sample is the best adsorbent which has most stable of chemical bonding and also has the most pores that influence an adsorption phenomena. Isotherm adsorption analysis showed that the adsorption mechanism of Cd and Ni ions onto the suface of PB, PT and PTM followed the Temkin and Langmuir isotherm adsorption. Adsorption ability of PTM is the best than the other PB and PT which can adsorps 256,23 mg Cd/g PTM and 87,45 mg Ni/g PTM in 500 ppm synthetic aqueous solution

Bond strength of repaired amalgam restorations.

PubMed

Rey, Rosalia; Mondragon, Eduardo; Shen, Chiayi

2015-01-01

This in vitro study investigated the interfacial flexural strength (FS) of amalgam repairs and the optimal combination of repair materials and mechanical retention required for a consistent and durable repair bond. Amalgam bricks were created, each with 1 end roughened to expose a fresh surface before repair. Four groups followed separate repair protocols: group 1, bonding agent with amalgam; group 2, bonding agent with composite resin; group 3, mechanical retention (slot) with amalgam; and group 4, slot with bonding agent and amalgam. Repaired specimens were stored in artificial saliva for 1, 10, 30, 120, or 360 days before being loaded to failure in a 3-point bending test. Statistical analysis showed significant changes in median FS over time in groups 2 and 4. The effect of the repair method on the FS values after each storage period was significant for most groups except the 30-day storage groups. Amalgam-amalgam repair with adequate condensation yielded the most consistent and durable bond. An amalgam bonding agent could be beneficial when firm condensation on the repair surface cannot be achieved or when tooth structure is involved. Composite resin can be a viable option for amalgam repair in an esthetically demanding region, but proper mechanical modification of the amalgam surface and selection of the proper bonding system are essential.

Effect of bacterial collagenase on resin-dentin bonds degradation.

PubMed

Toledano, Manuel; Osorio, Raquel; Osorio, Estrella; Aguilera, Fátima S; Yamauti, Monica; Pashley, David H; Tay, Franklin

2007-12-01

The objective of this study is to evaluate the effect of a bacterial collagenase on the degradation of resin-dentin bonds. Human dentin surfaces were bonded with: an etch-&-rinse self-priming adhesive (SB), a two-step self-etching primer/adhesive (SEB), and a 1-step self-etching adhesive (OUB). Composite build-ups were constructed. The bonded teeth were stored (24 h, 3 months, 1 year) in distilled water or in a buffered bacterial collagenase solution. Half of the specimens were stored as intact bonded teeth (Indirect Exposure/IE). The other half were sectioned into beams prior to storage (Direct Exposure/DE). After storage the intact teeth were sectioned into beams and all specimens were tested for microtensile bond strengths (MTBS). ANOVA and multiple comparisons tests were performed. Fractographic analysis was performed by scanning electron microscopy. The inclusion of bacterial collagenase in the storing solution did not lower the MTBS values over those seen in specimens stored in water. SB and SEB bonds strength were equal, and were superior to OUB. After 3 months of DE, SB and OUB bonded specimens showed decreases in MTBS; similar reductions required 1 year for SEB/DE. MTBS did not decrease in IE specimens except for OUB. Resin and collagen dissolution were evident in DE groups after storing.

Molecular structure, spectroscopic studies and first-order molecular hyperpolarizabilities of p-amino acetanilide.

PubMed

Abraham, Jose P; Sajan, D; Joe, I Hubert; Jayakumar, V S

2008-11-15

The infrared absorption, Raman spectra and SERS spectra of p-amino acetanilide have been analyzed with the aid of density functional theory calculations at B3LYP/6-311G(d,p) level. The electric dipole moment (mu) and the first hyperpolarizability (beta) values of the investigated molecule have been computed using ab initio quantum mechanical calculations. The calculation results also show that the synthesized molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. Computed geometries reveal that the PAA molecule is planar, while secondary amide group is twisted with respect to the phenyl ring is found, upon hydrogen bonding. The hyperconjugation of the C=O group with adjacent C-C bond and donor-acceptor interaction associated with the secondary amide have been investigated using computed geometry. The carbonyl stretching band position is found to be influenced by the tendency of phenyl ring to withdraw nitrogen lone pair, intermolecular hydrogen bonding, conjugation and hyperconjugation. The existence of intramolecular C=O...H hydrogen bonded have been investigated by means of the natural bonding orbital (NBO) analysis. The influence of the decrease of N-H and C=O bond orders and increase of C-N bond orders due to donor-acceptor interaction has been identified in the vibrational spectra. The SERS spectral analysis reveals that the large enhancement of in-plane bending, out of plane bending and ring breathing modes in the surface-enhanced Raman scattering spectrum indicates that the molecule is adsorbed on the silver surface in a 'atleast vertical' configuration, with the ring perpendicular to the silver surface.

Molecular structure, spectroscopic studies and first-order molecular hyperpolarizabilities of p-amino acetanilide

NASA Astrophysics Data System (ADS)

Abraham, Jose P.; Sajan, D.; Joe, I. Hubert; Jayakumar, V. S.

2008-11-01

The infrared absorption, Raman spectra and SERS spectra of p-amino acetanilide have been analyzed with the aid of density functional theory calculations at B3LYP/6-311G(d,p) level. The electric dipole moment ( μ) and the first hyperpolarizability ( β) values of the investigated molecule have been computed using ab initio quantum mechanical calculations. The calculation results also show that the synthesized molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. Computed geometries reveal that the PAA molecule is planar, while secondary amide group is twisted with respect to the phenyl ring is found, upon hydrogen bonding. The hyperconjugation of the C dbnd O group with adjacent C-C bond and donor-acceptor interaction associated with the secondary amide have been investigated using computed geometry. The carbonyl stretching band position is found to be influenced by the tendency of phenyl ring to withdraw nitrogen lone pair, intermolecular hydrogen bonding, conjugation and hyperconjugation. The existence of intramolecular C dbnd O⋯H hydrogen bonded have been investigated by means of the natural bonding orbital (NBO) analysis. The influence of the decrease of N-H and C dbnd O bond orders and increase of C-N bond orders due to donor-acceptor interaction has been identified in the vibrational spectra. The SERS spectral analysis reveals that the large enhancement of in-plane bending, out of plane bending and ring breathing modes in the surface-enhanced Raman scattering spectrum indicates that the molecule is adsorbed on the silver surface in a 'atleast vertical' configuration, with the ring perpendicular to the silver surface.

Study of distorted octahedral structure in 3d transition metal complexes using XAFS

NASA Astrophysics Data System (ADS)

Gaur, A.; Nitin Nair, N.; Shrivastava, B. D.; Das, B. K.; Chakrabortty, Monideepa; Jha, S. N.; Bhattacharyya, D.

2018-01-01

Distortion in octahedral structure of 3d transition metal complexes (Mn, Fe, Co, Ni, Cu, Zn) has been studied using XAFS showing divergent nature of Cu complex. EXAFS analysis showed elongated metal-oxygen bonds for Cu complex leading to more distorted structure. Derivative XANES spectrum at Cu K-edge exhibits splitting of main edge which is correlated to elongated Cu-O bond length. Using these coordination geometry around metal centers, theoretical XANES spectra have been generated and features observed have been correlated to the corresponding metals p-DOS. It has been shown that distorted octahedral field in Cu complex is responsible for splitting of p-DOS.

An Etic-Emic Analysis of Individualism and Collectivism.

ERIC Educational Resources Information Center

Triandis, Harry C.; And Others

1993-01-01

An analysis of the responses of 1,614 adult subjects from 10 cultures show that the Leung-Bond procedure provides ways of extracting both strong and weak etics relevant to individualism and weak etics relevant to collectivism. The most complete picture is obtained when both etics and emics are examined. (SLD)

Improvement of modulation bandwidth in electroabsorption-modulated laser by utilizing the resonance property in bonding wire.

PubMed

Kwon, Oh Kee; Han, Young Tak; Baek, Yong Soon; Chung, Yun C

2012-05-21

We present and demonstrate a simple and cost-effective technique for improving the modulation bandwidth of electroabsorption-modulated laser (EML). This technique utilizes the RF resonance caused by the EML chip (i.e., junction capacitance) and bonding wire (i.e, wire inductance). We analyze the effects of the lengths of the bonding wires on the frequency responses of EML by using an equivalent circuit model. To verify this analysis, we package a lumped EML chip on the sub-mount and measure its frequency responses. The results show that, by using the proposed technique, we can increase the modulation bandwidth of EML from ~16 GHz to ~28 GHz.

Formation of Si{sup 1+} in the early stages of the oxidation of the Si[001] 2 × 1 surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herrera-Gomez, Alberto, E-mail: aherrerag@cinvestav.mx; Aguirre-Tostado, Francisco-Servando; Pianetta, Piero

2016-03-15

The early stages of the oxidation of the Si[001] 2 × 1 surface were studied with synchrotron radiation photoelectron spectroscopy. The analysis was based on the block approach, which is a refinement of spectra-subtraction that accounts for changes on the background signal and for band-bending shifts. By this method, it was possible to robustly show that the formation of Si{sup 1+} is due to oxygen bonding to the upper dimer atoms. Our results contrast with ab initio calculation, which indicates that the most favorable bonding site is the back-bond of the down-dimer.

Long-term TEM analysis of the nanoleakage patterns in resin-dentin interfaces produced by different bonding strategies.

PubMed

Reis, Andre F; Giannini, Marcelo; Pereira, Patricia N R

2007-09-01

The aim of this study was to evaluate the ability of etch-and-rinse and self-etching adhesive systems to prevent time- and water-induced nanoleakage in resin-dentin interfaces over a 6-month storage period. Five commercial adhesives were tested, which comprise three different strategies of bonding resins to tooth hard tissues: one single-step self-etching adhesive (One-up Bond F (OB), Tokuyama); two two-step self-etching primers (Clearfil SE Bond (SE) and an antibacterial fluoride-containing system, Clearfil Protect Bond (CP), Kuraray Inc.); two two-step etch-and-rinse adhesives (Single Bond (SB), 3M ESPE and Prime&Bond NT (PB), Dentsply). Restored teeth were sectioned into 0.9 mm thick slabs and stored in water or mineral oil for 24 h, 3 or 6 months. A silver tracer solution was used to reveal nanometer-sized water-filled spaces and changes that occurred over time within resin-dentin interfaces. Characterization of interfaces was performed with the TEM. The two two-step self-etching primers showed little silver uptake during the 6-month experiment. Etch-and-rinse adhesives exhibited silver deposits predominantly within the hybrid layer (HL), which significantly increased for SB after water-storage. The one-step self-etching adhesive OB presented massive silver accumulation within the HL and water-trees protruding into the adhesive layer, which increased in size and quantity after water-storage. After storage in oil, reduced silver deposition was observed at the interfaces for all groups. Different levels of water-induced nanoleakage were observed for the different bonding strategies. The two-step self-etching primers, especially the antibacterial fluoride-containing system CP, showed the least nanoleakage after 6 months of storage in water.

Alkaline nanoparticle coatings improve resin bonding of 10-methacryloyloxydecyldihydrogenphosphate-conditioned zirconia.

PubMed

Qian, Mengke; Lu, Zhicen; Chen, Chen; Zhang, Huaiqin; Xie, Haifeng

Creating an alkaline environment prior to 10-methacryloyloxydecyldihydrogenphosphate (MDP) conditioning improves the resin bonding of zirconia. The present study evaluated the effects of four alkaline coatings with different water solubilities and pH values on resin bonding of MDP-conditioned zirconia. Two alkaline nanoparticle coatings were studied in particular. Thermodynamics calculations were performed to evaluate the strengths of MDP-tetragonal phase zirconia chemical bonds at different pH values. Zirconia surfaces with and without alkaline coatings were characterized by scanning electron microscope (SEM)/energy dispersive spectrometer and Fourier transform infrared spectroscopy; alkaline coatings included NaOH, Ca(OH) 2 , nano-MgO, and nano-Zr(OH) 4 . A shear bond strength (SBS) test was performed to evaluate the effects of the four alkaline coatings on bonding; the alkaline coatings were applied to the surfaces prior to conditioning the zirconia with MDP-containing primers. Gibbs free energies of the MDP-tetragonal zirconia crystal model coordination reaction in different pH environments were -583.892 (NaOH), -569.048 [Ca(OH) 2 ], -547.393 (MgO), and -530.279 kJ/mol [Zr(OH) 4 ]. Thermodynamic calculations indicated that the alkaline coatings improved bonding in the following order: NaOH > Ca(OH) 2 > MgO > Zr(OH) 4 . Statistical analysis of SBS tests showed a different result. SBSs were significantly different in groups that had different alkaline coatings, but it was not influenced by different primers. All four alkaline coatings increased SBS compared to control groups. Of the four coatings, nano-Zr(OH) 4 and -MgO showed higher SBS. Therefore, preparing nano-Zr(OH) 4 or -MgO coatings prior to conditioning with MDP-containing primers may potentially improve resin bonding of zirconia in the clinic.

Alkaline nanoparticle coatings improve resin bonding of 10-methacryloyloxydecyldihydrogenphosphate-conditioned zirconia

PubMed Central

Qian, Mengke; Lu, Zhicen; Chen, Chen; Zhang, Huaiqin; Xie, Haifeng

2016-01-01

Creating an alkaline environment prior to 10-methacryloyloxydecyldihydrogenphosphate (MDP) conditioning improves the resin bonding of zirconia. The present study evaluated the effects of four alkaline coatings with different water solubilities and pH values on resin bonding of MDP-conditioned zirconia. Two alkaline nanoparticle coatings were studied in particular. Thermodynamics calculations were performed to evaluate the strengths of MDP-tetragonal phase zirconia chemical bonds at different pH values. Zirconia surfaces with and without alkaline coatings were characterized by scanning electron microscope (SEM)/energy dispersive spectrometer and Fourier transform infrared spectroscopy; alkaline coatings included NaOH, Ca(OH)2, nano-MgO, and nano-Zr(OH)4. A shear bond strength (SBS) test was performed to evaluate the effects of the four alkaline coatings on bonding; the alkaline coatings were applied to the surfaces prior to conditioning the zirconia with MDP-containing primers. Gibbs free energies of the MDP-tetragonal zirconia crystal model coordination reaction in different pH environments were −583.892 (NaOH), −569.048 [Ca(OH)2], −547.393 (MgO), and −530.279 kJ/mol [Zr(OH)4]. Thermodynamic calculations indicated that the alkaline coatings improved bonding in the following order: NaOH > Ca(OH)2 > MgO > Zr(OH)4. Statistical analysis of SBS tests showed a different result. SBSs were significantly different in groups that had different alkaline coatings, but it was not influenced by different primers. All four alkaline coatings increased SBS compared to control groups. Of the four coatings, nano-Zr(OH)4 and -MgO showed higher SBS. Therefore, preparing nano-Zr(OH)4 or -MgO coatings prior to conditioning with MDP-containing primers may potentially improve resin bonding of zirconia in the clinic. PMID:27785013

Identifying Floppy and Rigid Regions in Proteins

NASA Astrophysics Data System (ADS)

Jacobs, D. J.; Thorpe, M. F.; Kuhn, L. A.

1998-03-01

In proteins it is possible to separate hard covalent forces involving bond lengths and bond angles from other weak forces. We model the microstructure of the protein as a generic bar-joint truss framework, where the hard covalent forces and strong hydrogen bonds are regarded as rigid bar constraints. We study the mechanical stability of proteins using FIRST (Floppy Inclusions and Rigid Substructure Topography) based on a recently developed combinatorial constraint counting algorithm (the 3D Pebble Game), which is a generalization of the 2D pebble game (D. J. Jacobs and M. F. Thorpe, ``Generic Rigidity: The Pebble Game'', Phys. Rev. Lett.) 75, 4051-4054 (1995) for the special class of bond-bending networks (D. J. Jacobs, "Generic Rigidity in Three Dimensional Bond-bending Networks", Preprint Aug (1997)). This approach is useful in identifying rigid motifs and flexible linkages in proteins, and thereby determines the essential degrees of freedom. We will show some preliminary results from the FIRST analysis on the myohemerythrin and lyozyme proteins.

The effect of disk type and cutting speed on the micro-tensile bond strength of ceramic specimens to resin cement.

PubMed

Castro, Martha C C; Sadek, Fernanda T; Batitucci, Eduardo; Miranda, Mauro S

2014-01-01

The bond strength of dental materials has been evaluated by tensile testing of micro-specimens. The cutting process used to obtain specimens may influence the results. The objective of this study was to investigate the influence of different types of diamond disks and cutting speeds on the bond strength of ceramic specimens and on specimen integrity. Lithium disilicate-based ceramic cubes were bonded with resin cement to composite resin cubes, according to the manufacturers' instructions. The ceramic/cement/resin blocks thus obtained were divided into two groups to be cut with Buehler(®) or Extec(®) disks and then sectioned at cutting speeds of 200 rpm and 400 rpm. The results showed that the bond strength values were affected by the cutting speed and disk/speed interaction (p<0.05). SEM analysis revealed better specimen properties when the blocks were cut at 200 rpm. It was concluded that ceramic specimens must be cut at low speeds.

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

NASA Astrophysics Data System (ADS)

Jörg, H.; Rösch, N.

The cluster Ni 2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the Ni-Ni distance fixed at the bulk value. The minimum energy is found at a Ni-C distance of 1.72 Å and a C-O bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm -1) shows reasonable agreement with EELS data (1810, 1870 cm -1), whereas the (Ni 2)-C frequency of 495 cm -1 is remarkably higher than the experimental values (380, 400 cm -1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a 1 orbital manifold exhibits strong antibonding effects.

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

NASA Astrophysics Data System (ADS)

Jörg, H.; Rösch, N.

1985-11-01

The cluster Ni 2CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm -1) shows reasonable agreement with EELS data (1810, 1870 cm -1), whereas the (Ni 2)C frequency of 495 cm -1 is remarkably higher than the experimental values (380, 400 cm -1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a 1orbital manifold exhibits strong antibonding effects.

Corrosion behaviour of friction-bit-joined and weld-bonded AA7075-T6/galvannealed DP980

DOE PAGES

Lim, Yong Chae; Squires, Lile; Pan, Tsung-Yu; ...

2016-12-22

Joining of aluminium alloys 7075-T6 and galvannealed dual phase 980 steel was achieved by friction bit joining (FBJ) and weld-bonding (FBJ + adhesive) processes. Accelerated laboratory-scale corrosion tests were performed on both FBJ only and weld-bonded specimens to study joint strength under a corrosive environment. Static lap shear tests showed that both FBJ only and weld-bonded cases generally retained more than 80% of the joint strength of non-corroded specimens at the end of corrosion testing. The presence of Zn/Fe coating on the steel substrate resulted in improved corrosion resistance for FBJ specimens, compared to joints produced with bare steel. Finally,more » an optical microscopy was used for cross-sectional analysis of corroded specimens. Some corrosion on the joining bit was observed near the bit head. However, the joining bit was still intact on the steel substrate, indicating that the primary bond was sound.« less

Symmetry and novelty in the electronic and geometric structure of nanoalloys:. the case of Ag27Cu7

NASA Astrophysics Data System (ADS)

Ortigoza, M. Alcántara; Rahman, T. S.

2008-04-01

Nanoparticles of bimetallic alloys have been shown to possess composition dependent characteristics which distinguish themselves from the corresponding bulk alloys. Taking the 34-atom nanoalloy of Ag and Cu (Ag27Cu7), we show using first principles electronic structure calculations that this core-shell alloy indeed has perfect D5h symmetry and consists of only 6 non-equivalent (2 Cu and 4 Ag) atoms. Analysis of the interatomic bond lengths and detailed electronic structure further reveal that the Cu atoms play a major role in controlling the characteristics of the nanoalloy. The higher cohesive energy, together with shorter bond length for Cu, compared to Ag, conspire to produce a hierarchy in the relative strengths of the Ag - Cu, Ag - Ag, and Cu - Cu bonds and corresponding interatomic bond lengths, point to the uniqueness in the characteristics of this nanoalloy. Charge density plots of Ag27Cu7 provide further insights into the relative strengths of the various interatomic bonds.

Corrosion behaviour of friction-bit-joined and weld-bonded AA7075-T6/galvannealed DP980

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, Yong Chae; Squires, Lile; Pan, Tsung-Yu

Joining of aluminium alloys 7075-T6 and galvannealed dual phase 980 steel was achieved by friction bit joining (FBJ) and weld-bonding (FBJ + adhesive) processes. Accelerated laboratory-scale corrosion tests were performed on both FBJ only and weld-bonded specimens to study joint strength under a corrosive environment. Static lap shear tests showed that both FBJ only and weld-bonded cases generally retained more than 80% of the joint strength of non-corroded specimens at the end of corrosion testing. The presence of Zn/Fe coating on the steel substrate resulted in improved corrosion resistance for FBJ specimens, compared to joints produced with bare steel. Finally,more » an optical microscopy was used for cross-sectional analysis of corroded specimens. Some corrosion on the joining bit was observed near the bit head. However, the joining bit was still intact on the steel substrate, indicating that the primary bond was sound.« less

Noble gas bond and the behaviour of XeO3 under pressure.

PubMed

Hou, Chunju; Wang, Xianlong; Botana, Jorge; Miao, Maosheng

2017-10-18

Over the past few decades, the concept of hydrogen bonds, in which hydrogen is electrophilic, has been extended to halogen bonds, chalcogen bonds and pnicogen bonds. Herein, we show that such a non-covalent bonding also exists in noble gas compounds. Using first principles calculations, we illustrate the OXe-O bond in molecular crystal XeO 3 and its effect on the behavior of this compound under pressure. Our calculations show that the covalent Xe-O bond lengths were elongated with increasing pressure and correspondingly the Xe-O stretching vibration frequencies were red shifted, which is similar to the change of H-bonds under pressure. The OXe-O bond and related hopping of O between neighboring Xe sites also correspond to the structural changes in the XeO 3 compounds at about 2 GPa. Our study extends the concept of hydrogen bonding to include all p-block elements and show a new bonding type for Noble gas elements in which it acts as an electrophilic species.

Heat treatment of pre-hydrolyzed silane increases adhesion of phosphate monomer-based resin cement to glass ceramic.

PubMed

de Carvalho, Rodrigo Furtado; Cotes, Caroline; Kimpara, Estevão Tomomitsu; Leite, Fabíola Pessoa Pereira; Özcan, Mutlu

2015-01-01

This study evaluated the influence of different forms of heat treatment on a pre-hydrolyzed silane to improve the adhesion of phosphate monomer-based (MDP) resin cement to glass ceramic. Resin and feldspathic ceramic blocks (n=48, n=6 for bond test, n=2 for microscopy) were randomly divided into 6 groups and subject to surface treatments: G1: Hydrofluoric acid (HF) 9.6% for 20 s + Silane + MDP resin cement (Panavia F); G2: HF 9.6% for 20 s + Silane + Heat Treatment (oven) + Panavia F; G3: Silane + Heat Treatment (oven) + Panavia F; G4: HF 9.6% for 20 s + Silane + Heat Treatment (hot air) + Panavia F; G5: Silane + Heat Treatment (hot air) + Panavia F; G6: Silane + Panavia F. Microtensile bond strength (MTBS) test was performed using a universal testing machine (1 mm/min). After debonding, the substrate and adherent surfaces were analyzed using stereomicroscope and scanning electron microscope (SEM) to categorize the failure types. Data were analyzed statistically using two-way test ANOVA and Tukey's test (=0.05). Heat treatment of the silane containing MDP, with prior etching with HF (G2: 13.15 ± 0.89a; G4: 12.58 ± 1.03a) presented significantly higher bond strength values than the control group (G1: 9.16 ± 0.64b). The groups without prior etching (G3: 10.47 ± 0.70b; G5: 9.47 ± 0.32b) showed statistically similar bond strength values between them and the control group (G1). The silane application without prior etching and heat treatment resulted in the lowest mean bond strength (G6: 8.05 ± 0.37c). SEM analysis showed predominantly adhesive failures and EDS analysis showed common elements of spectra (Si, Na, Al, K, O, C) characterizing the microstructure of the glass-ceramic studied. Heat treatment of the pre-hydrolyzed silane containing MDP in an oven at 100 °C for 2 min or with hot air application at 50 ± 5 ºC for 1 min, was effective in increasing the bond strength values between the ceramic and resin cement containing MDP.

Bonding performance of experimental bioactive/biomimetic self-etch adhesives doped with calcium-phosphate fillers and biomimetic analogs of phosphoproteins.

PubMed

Abuna, Gabriel; Feitosa, Victor P; Correr, Americo Bortolazzo; Cama, Giuseppe; Giannini, Marcelo; Sinhoreti, Mario A; Pashley, David H; Sauro, Salvatore

2016-09-01

This study examined the bonding performance and dentin remineralization potential of an experimental adhesive containing calcium-phosphate (Ca/P) micro-fillers, and self-etching primers doped with phosphoprotein biomimetic analogs (polyacrylic acid-(PAA) and/or sodium trimetaphosphate-(TMP)). Experimental self-etching primers doped with biomimetic analogs (PAA and/or TMP), and an adhesive containing Ca(2+), PO4(-3)-releasing micro-fillers (Ca/P) were formulated. Sound human dentin specimens were bonded and cut into sticks after aging (24h or 6 months) under simulated pulpal pressure (20cm H2O), and tested for microtensile bond strength (μTBS). Results were analyzed using two-way ANOVA and Tukey's test (p<0.05). Interfacial silver nanoleakage was assessed using SEM. Remineralization of EDTA-demineralized dentin was assessed through FTIR and TEM ultrastructural analysis. Application of the Ca/P-doped adhesive with or without dentin pre-treatments with the primer containing both biomimetic analogs (PAA and TMP) promoted stable μTBS over 6 months. Conversely, μTBS of the control primer and filler-free adhesive significantly decreased after 6 months. Nanoleakage decreased within the resin-dentin interfaces created using the Ca/P-doped adhesives. EDTA-demineralized dentin specimens treated the Ca/P-doped adhesive and the primer containing PAA and TMP showed phosphate uptake (FTIR analysis), as well as deposition of needle-like crystallites at intrafibrillar level (TEM analysis). The use of Ca/P-doped self-etching adhesives applied in combination with analogs of phosphoproteins provides durable resin-dentin bonds. This approach may represent a suitable bonding strategy for remineralization of intrafibrillar dentin collagen within the resin-dentin interface. Copyright © 2016 Elsevier Ltd. All rights reserved.

Organic salts formed by 2,4,6-triaminopyrimidine and selected carboxylic acids via a variety of hydrogen bonds: Synthons cooperation, and crystal structures

NASA Astrophysics Data System (ADS)

Xing, Peiqi; Li, Qingyun; Li, Yingying; Wang, Kunpeng; Zhang, Qi; Wang, Lei

2017-05-01

By using solvent evaporation method, 2,4,6-triaminopyrimidine (TAPI) is employed to crystallize with a variety of acids, including 3,5-dihydroxybenzoic acid (HDHBA), 3-nitrophthalic acid (H2NPA), 5-amino-2,4,6-triiodoisophthalic acid (H2ATIPIA), 2,5-dibromoterephthalic acid (H2DBTPA), 1,5-naphthalenedisulfonic acid (H2NDSA), sebacic acid (H2SA), 1,2,4-benzenetricarboxylic acid (H3BTA), and biphenyl-2,2‧,5,5'-tetracarboxylic acid (H4BPTA). In all eight complexes, protons are completely exchanged from O atom of acid to nitrogen of TAPI in 1, 3, 4, and, 5, partly transferred in 2, 6, 7, and 8. The crystal structure of all eight complexes exhibit that classical robust hydrogen bonds X-H⋯X (X = O/N) direct the molecular crystals to bind together in a stacking modes. Classical hydrogen bond Nsbnd H⋯O is participated in forming all eight organic salts, while hydrogen bonding Osbnd H⋯O are found in constructing the diversity structures in salts 1, 2, 3, 4, 6, and 7. The analysis shows that some classical supramolecular synthons, such as I R22(8), V R24(12), and VI S(6), are observed again in the construction of hydrogen-bonding networks. In the formation of layered and reticular structure, strong hydrogen bonds between water molecules and ligands having well-refined hydrogen atoms have been considered. Water molecules play an important role in building supramolecular structures of 1, 2, 3, 4, 7, and 8. Moreover, salts 1-8 are further characterized and analyzed by element analysis, infrared radiation, thermogravimetric analysis, proton nuclear magnetic resonance spectra, and mass spectra.

Strain engineering of van der Waals heterostructures.

PubMed

Vermeulen, Paul A; Mulder, Jefta; Momand, Jamo; Kooi, Bart J

2018-01-18

Modifying the strain state of solids allows control over a plethora of functional properties. The weak interlayer bonding in van der Waals (vdWaals) materials such as graphene, hBN, MoS 2 , and Bi 2 Te 3 might seem to exclude strain engineering, since strain would immediately relax at the vdWaals interfaces. Here we present direct observations of the contrary by showing growth of vdWaals heterostructures with persistent in-plane strains up to 5% and we show that strain relaxation follows a not yet reported process distinctly different from strain relaxation in three-dimensionally bonded (3D) materials. For this, 2D bonded Bi 2 Te 3 -Sb 2 Te 3 and 2D/3D bonded Bi 2 Te 3 -GeTe multilayered films are grown using Pulsed Laser Deposition (PLD) and their structure is monitored in situ using Reflective High Energy Electron Diffraction (RHEED) and post situ analysis is performed using Transmission Electron Microscopy (TEM). Strain relaxation is modeled and found to solely depend on the layer being grown and its initial strain. This insight demonstrates that strain engineering of 2D bonded heterostructures obeys different rules than hold for epitaxial 3D materials and opens the door to precise tuning of the strain state of the individual layers to optimize functional performance of vdWaals heterostructures.

The effect of dentine pre-treatment using bioglass and/or polyacrylic acid on the interfacial characteristics of resin-modified glass ionomer cements.

PubMed

Sauro, Salvatore; Watson, Timothy; Moscardó, Agustin Pascual; Luzi, Arlinda; Feitosa, Victor Pinheiro; Banerjee, Avijit

2018-06-01

To evaluate the effect of load-cycle aging and/or 6 months artificial saliva (AS) storage on bond durability and interfacial ultramorphology of resin-modified glass ionomer cement (RMGIC) applied onto dentine air-abraded using Bioglass 45S5 (BAG) with/without polyacrylic acid (PAA) conditioning. RMGIC (Ionolux, VOCO) was applied onto human dentine specimens prepared with silicon-carbide abrasive paper or air-abraded with BAG with or without the use of PAA conditioning. Half of bonded-teeth were submitted to load cycling (150,000 cycles) and half immersed in deionised water for 24 h. They were cut into matchsticks and submitted immediately to microtensile bond strength (μTBS) testing or 6 months in AS immersion and subsequently μTBS tested. Results were analysed statistically by two-way ANOVA and Student-Newman-Keuls test (α = 0.05). Fractographic analysis was performed using FE-SEM, while further RMGIC-bonded specimens were surveyed for interfacial ultramorphology characterisation (dye-assisted nanoleakage) using confocal microscopy. RMGIC applied onto dentine air-abraded with BAG regardless PAA showed no significant μTBS reduction after 6 months of AS storage and/or load cycling (p > 0.05). RMGIC-dentine interface showed no sign of degradation/nanoleakage after both aging regimens. Conversely, interfaces created in PAA-conditioned SiC-abraded specimens showed significant reduction in μTBS (p < 0.05) after 6 months of storage and/or load cycling with evident porosities within bonding interface. Dentine pre-treatment using BAG air-abrasion might be a suitable strategy to enhance the bonding performance and durability of RMGIC applied to dentine. The use of PAA conditioner in smear layer-covered dentine may increase the risk of degradation at the bonding interface. A combined dentine pre-treatment using bioglass followed by PAA may increase the bond strength and maintain it stable over time. Conversely, the use of PAA conditioning alone may offer no significant contribute to the immediate and prolonged bonding performance. Copyright © 2018 Elsevier Ltd. All rights reserved.

Metal-metal bonding and aromaticity in [M2(NHCHNH)3]2 (μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh).

PubMed

Yan, Xiuli; Meng, Lingpeng; Sun, Zheng; Li, Xiaoyan

2016-02-01

The nature of M-M bonding and aromaticity of [M2(NHCHNH)3]2(μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh) was investigated using atoms in molecules (AIM) theory, electron localization function (ELF), natural bond orbital (NBO) and molecular orbital analysis. These analyses led to the following main conclusions: in [M2(NHCHNH)3]2(μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh), the Nb-Nb, Ru-Ru, and Rh-Rh bonds belong to "metallic" bonds, whereas Mo-Mo and Tc-Tc drifted toward the "dative" side; all these bonds are partially covalent in character. The Nb-Nb, Mo-Mo, and Tc-Tc bonds are stronger than Ru-Ru and Rh-Rh bonds. The M-M bonds in [M2(NHCHNH)3]2(μ-S)2 are stronger than those in [M2(NHCHNH)3]2(μ-O)2 for M = Nb, Mo, Tc, and Ru. The NICS(1)ZZ values show that all of the studied molecules, except [Ru2(NHCHNH)3]2(μ-O)2, are aromaticity molecules. O-bridged compounds have more aromaticity than S-bridged compounds. Graphical Abstract Left Molecular graph, and right electron localization function (ELF) isosurface of [M2(NHCHNH)3]2(μ-E)2(E = O, S; M = Nb, Mo, Tc, Ru, Rh).

Compositional, Atomic and Molecular Analysis in Support of Materials Needs of the U.S. Air Force.

DTIC Science & Technology

1982-09-01

internally hydrogen-bonded monomer in .which the keto group is involved in the hydrogen bond but the acid carbonyl is not. 3 ) 3 - Bromopyruvic Acid...The spectra and structure of 3 - bromopyruvic acid were investigated and compared to those of pyruvic acid. It has been found that the spectra of 3 ...phase, cyclic monomer in dilute solution). The solid state spectra are quite different, however. The solid states spectra of 3 - bromopyruvic acid show a

Studies of Single Biomolecules, DNA Conformational Dynamics, and Protein Binding

DTIC Science & Technology

2008-07-11

Nucleotide Base pairs Hydrogen bonds FIG. 1: Ladder structure of DNA showing the Watson - Crick bonding of the bases A, T, G, and C which are suspended by a...protected against unwanted action of chemicals and proteins. The three-dimensional structure of DNA is the famed Watson - Crick double-helix, the equilibrium...quantitative analysis [88]. [1] A. Kornberg and T. A. Baker, DNA Replication (W. H. Freeman, New York, 1992). [2] J. D. Watson and F. H. C. Crick

Metal–Metal Bonding in Uranium–Group 10 Complexes

PubMed Central

2016-01-01

Heterobimetallic complexes containing short uranium–group 10 metal bonds have been prepared from monometallic IUIV(OArP-κ2O,P)3 (2) {[ArPO]− = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U–M bond in IUIV(μ-OArP-1κ1O,2κ1P)3M0, M = Ni (3–Ni), Pd (3–Pd), and Pt (3–Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3–Ni with two further U–Ni complexes XUIV(μ-OArP-1κ1O,2κ1P)3Ni0, X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U–M bonds are significantly shorter than any other crystallographically characterized d–f-block bimetallic, even though the ligand flexes to allow a variable U–M separation. Excellent agreement is found between the experimental and computed structures for 3–Ni and 3–Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U–M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U–Ni bond than U–Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U–X adducts 3–Ni, 4, and 5. The data show a trend in uranium–metal bond strength that decreases from 3–Ni down to 3–Pt and suggest that exchanging the iodide for a fluoride strengthens the metal–metal bond. Despite short U–TM (transition metal) distances, four other computational approaches also suggest low U–TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3–Pd than 3–Ni, consistent with slightly larger U–TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal longer and weaker unsupported U–TM bonds vs 3. PMID:26942560

Effect of a bonding agent on in vitro biochemical activities of remineralizing resin-based calcium phosphate cements.

PubMed

Dickens, Sabine H; Flaim, Glenn M

2008-09-01

To test whether fluoride in a resin-based Ca-PO4 ion releasing cement or coating with an acidic bonding agent for improved adhesion compromised the cement remineralization potential. Cements were formulated without fluoride (Cement A) or with fluoride (Cement B). The treatment groups were A=Cement A; A2=Cement A+bonding agent; B=Cement B; B2=Cement B+bonding agent. The calcium, phosphate, and fluoride ion release in saliva-like solution (SLS) was determined from hardened cement disks without or with a coating of bonding agent. For the remineralization, two cavities were prepared in dentin of extracted human molars and demineralized. One cavity received composite resin (control); the other received treatment A, A2, B or B2. After 6 week incubation in SLS, 180 microm cross-sections were cut. The percentage remineralization was determined by transverse microradiography comparing the dentin mineral density under the cement to that under the control. The percentage of remineralization (mean+/-S.D.) was A (39+/-14)=B (37+/-18), A2 (23+/-13), B2 (14+/-7). Two-way analysis of variance (ANOVA) and Holm-Sidak test showed a significant effect from the presence of bonding agent (p<0.05), but not from fluoride (p>0.05). The ion solution concentrations of all groups showed undersaturation with respect to dicalcium phosphate dihydrate and calcium fluoride and supersaturation for fluorapatite and hydroxyapatite suggesting a positive remineralization potential. Compared to the control all treatments resulted in mineral increase. The remineralization was negatively affected by the presence of the bonding agent.

Bond Stability of a Universal Adhesive System to Eroded/Abraded Dentin After Deproteinization.

PubMed

Augusto, M G; Torres, Crg; Pucci, C R; Schlueter, N; Borges, A B

Erosive/abrasive challenges can potentially compromise bonding to dentin. Aiming to improve the quality and stability of bonding to this substrate, this study investigated the combined effect of erosion and toothbrush abrasion on the microtensile bond strength (μTBS) stability to dentin using a universal adhesive system in total and self-etching modes, associated or not associated with deproteinization. Bovine dentin specimens were divided into five groups according to the organic matrix condition (n=20): control (C); erosion (E); erosion + abrasion (EA); erosion + sodium hypochlorite (EH); erosion + abrasion + sodium hypochlorite (EAH). The groups were further divided (n=10) according to the mode of application (total or self-etching) of a universal adhesive. After the bonding procedure, composite blocks were built up, and the samples were cut to obtain sticks for μTBS testing. For each specimen, one-half of the sticks was immediately tested, and the other one-half was tested after artificial aging (5000 thermocycles, 5°C and 55°C). Three-way analysis of variance (α=5%) showed a significant difference for the triple interaction ( p=0.0007). Higher μTBS means were obtained for the EH and EAH groups compared with the E and EA groups. The control group showed immediate μTBS values similar to that of the E and EA groups for both bond strategies. Erosion and erosion/abrasion did not significantly influence the immediate μTBS to dentin. Artificial aging reduced μTBS values for the groups C, E, and EA using the total-etching mode. Deproteinization maintained the bond stability to artificially aged eroded and eroded/abraded dentin.

77 FR 43740 - Changes to the In-Bond Process; Correction

Federal Register 2010, 2011, 2012, 2013, 2014

2012-07-26

... various changes to the in-bond regulations to enhance CBP's ability to regulate and track in-bond...-bond merchandise is exported. In that document, CBP published a summary of its analysis under the Regulatory Flexibility Act and stated that the complete Initial Regulatory Flexibility Analysis (IRFA) was...

Evaluation of Effect of Zirconia Surface Treatment, Using Plasma of Argon and Silane, on the Shear Bond Strength of Two Composite Resin Cements

PubMed Central

Ramdev, Poojya; Shruthi, C S

2017-01-01

Introduction Yttria stabilised tetragonal zirconia opens new vistas for all ceramic restoration by the mechanism of transformation toughening, making it much stronger compared to all other ceramic materials. Currently, it is the most recent core material for all ceramic fixed partial dentures due to its ability to withstand high simulated masticatory loads. Problems which have been reported with zirconia restorations involve the core cement interface leading to loss of retention of the prosthesis. Different reasons which have been reported for the same include the lack of adhesion between zirconia and commonly used cements due to absence of silica phase which makes zirconia not etchable. In addition, the hydrophobic nature of zirconia causes low wettability of zirconia surface by the adhesive cements which are commonly used. Aim The purpose of this in vitro study was to compare and evaluate the effect of two pre-treatments of zirconia, using plasma of argon and silane, on the shear bond strength values of two composite resin cements to zirconia and to evaluate the failure pattern of the debonded areas using stereomicroscopic analysis. Materials and Methods Sixty zirconia discs (10 mm×2 mm) were randomly divided into three groups (n=20), following surface treatment, with airborne particle abrasion, using 110 µm Al2O3: Group I (control), Group II (plasma of argon cleaning), and Group III (application of silane primer). Each group had two subgroups based on the type of resin cement used for bonding: subgroup A; Rely X Ultimate (3M ESPE) and subgroup B; Panavia F (Kuraray). In subgroup A, Rely X universal silane primer and in subgroup B Clearfil ceramic primer was used. Shear bond strengths were determined after water storage for one day and thermocycling for 5000 cycles. Data (megapascal) were analyzed using ANOVA and Bonferroni test. Specimens were subjected to stereomicroscopic analysis, for evaluation of failure pattern. Results Group III produced the highest shear bond strength followed by Group II and Group I. Subgroup A showed higher shear bond strength than Subgroup B. Stereomicroscopic analysis showed cohesive failure in Group III, while in Group I adhesive failure was seen. Conclusion Silane primer application caused maximum increase in shear bond strength due to increased wettability. Argon plasma treatment was less effective in comparison to silane treatment. Air abrasion when used alone resulted in lower bond strength values, thereby making it necessary to use a combination of surface treatments. Rely X Ultimate cement was superior to Panavia F in terms of adhesive bonding to zirconia. PMID:28969271

Microscopic progression in the free radical addition reaction: modeling, geometry, energy, and kinetics.

PubMed

Zhang, Yun; Huang, Hong; Liang, Zhiling; Liu, Houhe; Yi, Ling; Zhang, Jinhong; Zhang, Zhiqiang; Zhong, Cheng; Huang, Yugang; Ye, Guodong

2017-03-01

The free radical addition reaction is very important in UV curing. The benzoyl radical is the most commonly observed radical. In the addition process, the benzoyl radical adds to an acrylate monomer, forming a primary radical that has great value for subsequent research. In this article, a quantum chemical method was used to study the microscopic progression from the reactive complex to the saddle point. The reactions of three monomers (amylene, allyl methyl ether and methyl acrylate) with a benzoyl radical were evaluated in terms of geometry and energy. The results were also interpreted with an expanded version of the Polanyi rules and the interaction/deformation theory. The deformation energy of methyl acrylate was found to be the smallest, and the bond formation index showed that the transition state in the methyl acrylate system forms early, and can easily reach the saddle point. The activity of the monomer was ascertained by charge analysis and was further confirmed by the reaction rate. Mayer bond order curves depicted the constantly changing chemical bonds during formation and dissociation. Reduced density gradient analysis showed a weak interaction between the monomer and the benzoyl radical.

Bond Strength and Interfacial Morphology of Different Dentin Adhesives in Primary Teeth

PubMed Central

Vashisth, Pallavi; Mittal, Mudit; Goswami, Mousumi; Chaudhary, Seema; Dwivedi, Swati

2014-01-01

Objective: To evaluate the interfacial morphology and the bond strength produced by the three-step, two-step and single-step bonding systems in primary teeth. Materials and Methods: Occlusal surfaces of 72 extracted human deciduous teeth were ground to expose the dentin. The teeth were divided into four groups: (a) Scotchbond Multipurpose (3M, ESPE), (b) Adh Se (Vivadent), (d) OptiBond All-in-One (Kerr) and (e)Futurabond NR (VOCO, Cuxhaven, Germany). The adhesives were applied to each group following the manufacturer’s instructions. Then, teeth from each group were divided into two groups: (A) For viewing interfacial morphology (32 teeth), with 8 teeth in each group, and (B) For measurement of bond strength (40 teeth), with 10 teeth in each group. All the samples were prepared for viewing under SEM. The statistical analysis was done using SPSS version 15.0 software. Results: Observational measurement of tag length in different adhesives revealed that Scotchbond had the most widely spread values with a range from 12.20 to 89.10μm while OptiBond AIO had the narrowest range (0 to 22.50). The bond strength of Scotchbond Multipurpose was significantly higher (7.4744±1.88763) (p<0.001) as compared to Futurabond NR (3.8070±1.61345), Adhe SE (4.4478 ± 1.3820) and OptiBond-all-in-one (4.4856±1.07925). Conclusion: The three-step bonding system showed better results as compared to simplified studied bonding systems PMID:24910694

Modeling single molecule junction mechanics as a probe of interface bonding

NASA Astrophysics Data System (ADS)

Hybertsen, Mark S.

2017-03-01

Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. A set of exemplary model junction structures has been analyzed using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond to the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N-Au and S-Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor-acceptor bond formation at the junction interfaces. The force extension characteristic of longer molecules such as diaminooctane, where the dipole interaction effects drop to a negligible level, accurately fit to the renormalized single-bond potential form. The results suggest that measured force extension characteristics for single molecule junctions could be analyzed with a modified potential form that accounts for the energy stored in deformable mechanical components in series.

Modeling single molecule junction mechanics as a probe of interface bonding

DOE PAGES

Hybertsen, Mark S.

2017-03-07

Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. We analyzed a set of exemplary model junction structures using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond tomore » the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N–Au and S–Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This, then, allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor-acceptor bond formation at the junction interfaces. The force extension characteristic of longer molecules such as diaminooctane, where the dipole interaction effects drop to a negligible level, accurately fit to the renormalized single-bond potential form. Our results suggest that measured force extension characteristics for single molecule junctions could be analyzed with a modified potential form that accounts for the energy stored in deformable mechanical components in series.« less

Modeling single molecule junction mechanics as a probe of interface bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hybertsen, Mark S.

Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. We analyzed a set of exemplary model junction structures using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond tomore » the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N–Au and S–Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This, then, allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor-acceptor bond formation at the junction interfaces. The force extension characteristic of longer molecules such as diaminooctane, where the dipole interaction effects drop to a negligible level, accurately fit to the renormalized single-bond potential form. Our results suggest that measured force extension characteristics for single molecule junctions could be analyzed with a modified potential form that accounts for the energy stored in deformable mechanical components in series.« less

Tracing the Fingerprint of Chemical Bonds within the Electron Densities of Hydrocarbons: A Comparative Analysis of the Optimized and the Promolecule Densities.

PubMed

Keyvani, Zahra Alimohammadi; Shahbazian, Shant; Zahedi, Mansour

2016-10-18

The equivalence of the molecular graphs emerging from the comparative analysis of the optimized and the promolecule electron densities in two hundred and twenty five unsubstituted hydrocarbons was recently demonstrated [Keyvani et al. Chem. Eur. J. 2016, 22, 5003]. Thus, the molecular graph of an optimized molecular electron density is not shaped by the formation of the C-H and C-C bonds. In the present study, to trace the fingerprint of the C-H and C-C bonds in the electron densities of the same set of hydrocarbons, the amount of electron density and its Laplacian at the (3, -1) critical points associated with these bonds are derived from both optimized and promolecule densities, and compared in a newly proposed comparative analysis. The analysis not only conforms to the qualitative picture of the electron density build up between two atoms upon formation of a bond in between, but also quantifies the resulting accumulation of the electron density at the (3, -1) critical points. The comparative analysis also reveals a unified mode of density accumulation in the case of 2318 studied C-H bonds, but various modes of density accumulation are observed in the case of 1509 studied C-C bonds and they are classified into four groups. The four emerging groups do not always conform to the traditional classification based on the bond orders. Furthermore, four C-C bonds described as exotic bonds in previous studies, for example the inverted C-C bond in 1,1,1-propellane, are naturally distinguished from the analysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raupach, Marc; Tonner, Ralf, E-mail: tonner@chemie.uni-marburg.de

The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the additionmore » of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H{sub 2} on M(001), M = Pd, Cu), and semiconducting (CO and C{sub 2}H{sub 2} on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.« less

Dicalcium phosphate (CaHPO4·2H2O) precipitation through ortho- or meta-phosphoric acid-etching: effects on the durability and nanoleakage/ultra-morphology of resin-dentine interfaces.

PubMed

Feitosa, Victor Pinheiro; Bazzocchi, Maria Giulia; Putignano, Angelo; Orsini, Giovanna; Luzi, Arlinda Luzi; Sinhoreti, Mário Alexandre Coelho; Watson, Timothy F; Sauro, Salvatore

2013-11-01

To compare the effects of two etching procedures using meta-phosphoric (MPA) or ortho-phosphoric acid (OPA) on dentine demineralisation, resin-dentine bonds durability and interface nanoleakage/ultra-morphology. Middle-dentine specimens were etched using 37% OPA (15s) or 40% MPA (60s) and submitted to infrared spectroscopy (FTIR) or ultra-morphology dye-assisted (calcium-staining) confocal microscopy (Ca-CLSM). A three-step etch-and-rinse adhesive was formulated, applied onto dentine and light-cured for 30s before composite build-up. After 24h, the dentine-bonded specimens were cut into 1mm(2) beams; half were immediately submitted to microtensile bond strength (μTBS) and half stored in DW for six months. The μTBS results were analysed with repeated-measures ANOVA and Tukey's test (p<0.05). Further teeth were bonded and prepared for interface nanoleakage/ultra-morphology confocal evaluation. FTIR and Ca-CLSM analyses showed dicalcium phosphate dihydrate (Brushite) precipitation in MPA-etched dentine and on the bottom (front of demineralisation) of the OPA-etched dentine. Statistical analysis showed similar μTBS for both etching procedures after 24h. The μTBS of specimens in OPA-group dropped significantly (p<0.05) after six month; the specimens in the MPA group showed no statistically difference (p>0.05). CLSM depicted no evident sign of nanoleakage within the resin-dentine interface of the MPA-treated specimens, while the specimens in OPA-group presented intense nanoleakage and interface degradation. The use of MPA (60s) as an alternative dentine conditioning agent in etch-and-rinse bonding procedures may be a suitable strategy to create more durable resin-dentine bonds. Copyright © 2013 Elsevier Ltd. All rights reserved.

Preliminary assessment of metal-porcelain bonding strength of CoCrW alloy after 3wt.% Cu addition.

PubMed

Lu, Yanjin; Zhao, Chaoqian; Ren, Ling; Guo, Sai; Gan, Yiliang; Yang, Chunguang; Wu, Songquan; Lin, Junjie; Huang, Tingting; Yang, Ke; Lin, Jinxin

2016-06-01

In this work, a novel Cu-bearing CoCrW alloy fabricated by selective laser melting for dental application has been studied. For its successful application, the bonding strength of metal-porcelain is essential to be systematically investigated. Therefore, the aim of this study was to evaluate the metal-porcelain bonding strength of CoCrWCu alloy by three-point bending test, meanwhile the Ni-free CoCrW alloy was used as control. The oxygen content was investigated by an elemental analyzer; X-ray photoelectron spectroscopy (XPS) was used to analyze the surface chemical composition of CoCrW based alloy after preoxidation treatment; the fracture mode was investigated by X-ray energy spectrum analysis (EDS) and scanning electron microscope (SEM). Result from the oxygen content analysis showed that the content of oxygen dramatically increased after the Cu addition. And the XPS suggested that Co-oxidation, Cr2O3, CrO2, WO3, Cu2O and CuO existed on the preoxidated surface of the CoCrWCu alloy; the three-point bending test showed that the bonding strength of the CoCrWCu alloy was 43.32 MPa, which was lower than that of the CoCrW group of 47.65 MPa. However, the average metal-porcelain bonding strength is significantly higher than the minimum value in the ISO 9693 standard. Results from the SEM images and EDS indicated that the fracture mode of CoCrWCu-porcelain was mixed between cohesive and adhesive. Based on the results obtained in this study, it can be indicated that the Cu-bearing CoCrW alloy fabricated by the selective laser melting is a promising candidate for use in dental application. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of Hydrofluoric Acid Concentration on Resin Adhesion to a Feldspathic Ceramic.

PubMed

Venturini, Andressa Borin; Prochnow, Catina; Rambo, Dagma; Gundel, Andre; Valandro, Luiz Felipe

2015-08-01

To evaluate the effect of different concentrations of hydrofluoric acid (HF) on the contact angle and the resin bond strength durability to feldspathic ceramic. To evaluate the contact angles of distilled water on etched feldspathic ceramic, 25 specimens (12×10×2.4 mm) of VitaBlocks Mark II were used, divided into 5 groups (n=5): one unconditioned control (UC) group with no ceramic surface treatment, and 4 other groups that were etched for 60 s with different concentrations of HF: 1% (HF1), 3% (HF3), 5% (HF5) and 10% (HF10). The bond testing utilized 40 ceramic blocks (12×10×4 mm) that were fabricated and subjected to the same surface treatments as previously mentioned (excluding the control). The etched surfaces were silanized and resin cement was applied. After 24 h, the blocks were sectioned to produce bar specimens that were divided into two groups, non-aged (immediate testing) and aged (storage for 230 days+12,000 thermocycles at 5°C and 55°C), and subjected to microtensile testing (μTBS). Micromorphogical analysis of the treated surfaces was also performed (atomic force and scanning electron microscopy). One-way ANOVA and Tukey's tests were applied for data analysis. UC had the highest contact angle (61.4°), whereas HF10 showed the lowest contact angle (17.5°). In non-aged conditions, different acids promoted statistically similar bond strengths (14.2 to 15.7 MPa) (p>0.05); in terms of bond durability, only the bond strength of the HF1 group presented a statistically significant decrease comparing before and after aging (14.5 to 10.2 MPa). When etched with 3%, 5%, or 10% hydrofluoric acid, the ceramic tested showed stable resin adhesion after long-term aging.

Polymer complexes. LVII. Supramolecular assemblies of novel polymer complexes of dioxouranium(VI) with some substituted allyl azo dye compounds

NASA Astrophysics Data System (ADS)

Diab, M. A.; El-Sonbati, A. Z.; El-Bindary, A. A.; Balboula, M. Z.

2013-05-01

A novel method to synthesize some dioxouranium(VI) polymer complexes of the general formula [UO2(Ln)2(OAc)2] (where HLn = azo allyl rhodanine). The structure of the novel mononuclear dioxoutranium(VI) polymer complexes was characterized using elemental analysis, spectral (electronic, infrared, 1H &13C NMR) studies, magnetic susceptibility measurements and thermal analysis. The molar conductivities show that all the polymer complexes are non-electrolytes. The IR showed that the ligand HLn act as bidentate neutral through carbonyl group and imine group nitrogen atom forming thereby a six-membered chelating ring and concomitant formation of an intramolecular hydrogen bond. The υ3 frequency of UO2+2 has been shown to be an excellent molecular probe for studying the coordinating power of the ligands. The values of υ3 of the prepared complexes containing UO2+2 were successfully used to calculate the force constant, FUO (10-8 N/Å) and the bond length RUO (Å) of the Usbnd O bond. A strategy based upon both theoretical and experimental investigations has been adopted. The theoretical aspects are described in terms of the well-known theory of 5d-4f transitions. Wilson's, matrix method, Badger's formula, and Jones and El-Sonbati equations were used to calculate the Usbnd O bond distances from the values of the stretching and interaction force constants. The most probable correlation between Usbnd O force constant to Usbnd O bond distance were satisfactorily discussed in term of Badger's rule and the equations suggested by Jones and El-Sonbati. The effect of Hammet constant is also discussed.

Bonded composite to metal scarf joint performance in an aircraft landing gear drag strut. [for Boeing 747 aircraft

NASA Technical Reports Server (NTRS)

Howell, W. E.

1974-01-01

The structural performance of a boron-epoxy reinforced titanium drag strut, which contains a bonded scarf joint and was designed to the criteria of the Boeing 747 transport, was evaluated. An experimental and analytical investigation was conducted. The strut was exposed to two lifetimes of spectrum loading and was statically loaded to the tensile and compressive design ultimate loads. Throughout the test program no evidence of any damage in the drag strut was detected by strain gage measurements, ultrasonic inspection, or visual observation. An analytical study of the bonded joint was made using the NASA structural analysis computer program NASTRAN. A comparison of the strains predicted by the NASTRAN computer program with the experimentally determined values shows excellent agreement. The NASTRAN computer program is a viable tool for studying, in detail, the stresses and strains induced in a bonded joint.

Conformational dynamics of L-lysine, L-arginine, L-ornithine binding protein reveals ligand-dependent plasticity.

PubMed

Silva, Daniel-Adriano; Domínguez-Ramírez, Lenin; Rojo-Domínguez, Arturo; Sosa-Peinado, Alejandro

2011-07-01

The molecular basis of multiple ligand binding affinity for amino acids in periplasmic binding proteins (PBPs) and in the homologous domain for class C G-protein coupled receptors is an unsolved question. Here, using unrestrained molecular dynamic simulations, we studied the ligand binding mechanism present in the L-lysine, L-arginine, L-ornithine binding protein. We developed an analysis based on dihedral angles for the description of the conformational changes upon ligand binding. This analysis has an excellent correlation with each of the two main movements described by principal component analysis (PCA) and it's more convenient than RMSD measurements to describe the differences in the conformational ensembles observed. Furthermore, an analysis of hydrogen bonds showed specific interactions for each ligand studied as well as the ligand interaction with the aromatic residues Tyr-14 and Phe-52. Using uncharged histidine tautomers, these interactions are not observed. On the basis of these results, we propose a model in which hydrogen bond interactions place the ligand in the correct orientation to induce a cation-π interaction with Tyr-14 and Phe-52 thereby stabilizing the closed state. Our results also show that this protein adopts slightly different closed conformations to make available specific hydrogen bond interactions for each ligand thus, allowing a single mechanism to attain multiple ligand specificity. These results shed light on the experimental evidence for ligand-dependent conformational plasticity not explained by the previous crystallographic data. Copyright © 2011 Wiley-Liss, Inc.

Comparison of bond strengths of ceramic brackets bonded to zirconia surfaces using different zirconia primers and a universal adhesive.

PubMed

Lee, Ji-Yeon; Ahn, Jaechan; An, Sang In; Park, Jeong-Won

2018-02-01

The aim of this study is to compare the shear bond strengths of ceramic brackets bonded to zirconia surfaces using different zirconia primers and universal adhesive. Fifty zirconia blocks (15 × 15 × 10 mm, Zpex, Tosoh Corporation) were polished with 1,000 grit sand paper and air-abraded with 50 µm Al 2 O 3 for 10 seconds (40 psi). They were divided into 5 groups: control (CO), Metal/Zirconia primer (MZ, Ivoclar Vivadent), Z-PRIME Plus (ZP, Bisco), Zirconia Liner (ZL, Sun Medical), and Scotchbond Universal adhesive (SU, 3M ESPE). Transbond XT Primer (used for CO, MZ, ZP, and ZL) and Transbond XT Paste was used for bracket bonding (Gemini clear ceramic brackets, 3M Unitek). After 24 hours at 37°C storage, specimens underwent 2,000 thermocycles, and then, shear bond strengths were measured (1 mm/min). An adhesive remnant index (ARI) score was calculated. The data were analyzed using one-way analysis of variance and the Bonferroni test ( p = 0.05). Surface treatment with primers resulted in increased shear bond strength. The SU group showed the highest shear bond strength followed by the ZP, ZL, MZ, and CO groups, in that order. The median ARI scores were as follows: CO = 0, MZ = 0, ZP = 0, ZL = 0, and SU = 3 ( p < 0.05). Within this experiment, zirconia primer can increase the shear bond strength of bracket bonding. The highest shear bond strength is observed in SU group, even when no primer is used.

Comparison of bond strengths of ceramic brackets bonded to zirconia surfaces using different zirconia primers and a universal adhesive

PubMed Central

2018-01-01

Objectives The aim of this study is to compare the shear bond strengths of ceramic brackets bonded to zirconia surfaces using different zirconia primers and universal adhesive. Materials and Methods Fifty zirconia blocks (15 × 15 × 10 mm, Zpex, Tosoh Corporation) were polished with 1,000 grit sand paper and air-abraded with 50 µm Al2O3 for 10 seconds (40 psi). They were divided into 5 groups: control (CO), Metal/Zirconia primer (MZ, Ivoclar Vivadent), Z-PRIME Plus (ZP, Bisco), Zirconia Liner (ZL, Sun Medical), and Scotchbond Universal adhesive (SU, 3M ESPE). Transbond XT Primer (used for CO, MZ, ZP, and ZL) and Transbond XT Paste was used for bracket bonding (Gemini clear ceramic brackets, 3M Unitek). After 24 hours at 37°C storage, specimens underwent 2,000 thermocycles, and then, shear bond strengths were measured (1 mm/min). An adhesive remnant index (ARI) score was calculated. The data were analyzed using one-way analysis of variance and the Bonferroni test (p = 0.05). Results Surface treatment with primers resulted in increased shear bond strength. The SU group showed the highest shear bond strength followed by the ZP, ZL, MZ, and CO groups, in that order. The median ARI scores were as follows: CO = 0, MZ = 0, ZP = 0, ZL = 0, and SU = 3 (p < 0.05). Conclusions Within this experiment, zirconia primer can increase the shear bond strength of bracket bonding. The highest shear bond strength is observed in SU group, even when no primer is used. PMID:29487838

Evaluation of an alternative technique to optimize direct bonding of orthodontic brackets to temporary crowns.

PubMed

Dias, Francilena Maria Campos Santos; Pinzan-Vercelino, Célia Regina Maio; Tavares, Rudys Rodolfo de Jesus; Gurgel, Júlio de Araújo; Bramante, Fausto Silva; Fialho, Melissa Nogueira Proença

2015-01-01

To compare shear bond strength of different direct bonding techniques of orthodontic brackets to acrylic resin surfaces. The sample comprised 64 discs of chemically activated acrylic resin (CAAR) randomly divided into four groups: discs in group 1 were bonded by means of light-cured composite resin (conventional adhesive); discs in group 2 had surfaces roughened with a diamond bur followed by conventional direct bonding by means of light-cured composite resin; discs in group 3 were bonded by means of CAAR (alternative adhesive); and discs in group 4 had surfaces roughened with a diamond bur followed by direct bonding by means of CAAR. Shear bond strength values were determined after 24 hours by means of a universal testing machine at a speed of 0.5 mm/min, and compared by analysis of variance followed by post-hoc Tukey test. Adhesive remnant index (ARI) was measured and compared among groups by means of Kruskal-Wallis and Dunn tests. Groups 3 and 4 had significantly greater shear bond strength values in comparison to groups 1 and 2. Groups 3 and 4 yielded similar results. Group 2 showed better results when compared to group 1. In ARI analyses, groups 1 and 2 predominantly exhibited a score equal to 0, whereas groups 3 and 4 predominantly exhibited a score equal to 3. Direct bonding of brackets to acrylic resin surfaces using CAAR yielded better results than light-cured composite resin. Surface preparation with diamond bur only increased shear bond strength in group 2.

Experimental etch-and-rinse adhesives doped with bioactive calcium silicate-based micro-fillers to generate therapeutic resin-dentin interfaces.

PubMed

Profeta, A C; Mannocci, F; Foxton, R; Watson, T F; Feitosa, V P; De Carlo, B; Mongiorgi, R; Valdré, G; Sauro, S

2013-07-01

This study aimed at evaluating the therapeutic bioactive effects on the bond strength of three experimental bonding agents containing modified Portland cement-based micro-fillers applied to acid-etched dentin and submitted to aging in simulated body fluid solution (SBS). Confocal laser (CLSM) and scanning electron microscopy (SEM) were also performed. A type-I ordinary Portland cement was tailored using different compounds such as sodium-calcium-aluminum-magnesium silicate hydroxide (HOPC), aluminum-magnesium-carbonate hydroxide hydrates (HCPMM) and titanium oxide (HPCTO) to create three bioactive micro-fillers. A resin blend mainly constituted by Bis-GMA, PMDM and HEMA was used as control (RES-Ctr) or mixed with each micro-filler to create three experimental bonding agents: (i) Res-HOPC, (ii) Res-HCPMM and (iii) Res-HPCTO. The bonding agents were applied onto 37% H3PO4-etched dentin and light-cured for 30s. After build-ups, they were prepared for micro-tensile bond strength (μTBS) and tested after 24h or 6 months of SBS storage. SEM analysis was performed after de-bonding, while CLSM was used to evaluate the ultra-morphology/nanoleakage and the mineral deposition at the resin-dentin interface. High μTBS values were achieved in all groups after 24h. Only Res-HOPC and Res-HCPMM showed stable μTBS after SBS storage (6 months). All the resin-dentin interfaces created using the bonding agents containing the bioactive micro-fillers tested in this study showed an evident reduction of nanoleakage and mineral deposition after SBS storage. Resin bonding systems containing specifically tailored Portland cement micro-fillers may promote a therapeutic mineral deposition within the hybrid layer and increase the durability of the resin-dentin bond. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Influence of intraoral temperature and relative humidity on the dentin bond strength: an in situ study.

PubMed

Saraiva, Letícia O; Aguiar, Thaiane R; Costa, Leonardo; Cavalcanti, Andrea N; Giannini, Marcelo; Mathias, Paula

2015-01-01

The effect of the intraoral environment during adhesive restorative procedures remains a concern, especially in the absence of rubber dam isolation. To evaluate the temperature and relative humidity (RH) at anterior and posterior intraoral sites and their effects on the dentin bond strength of two-step etch-and-rinse adhesive systems. Sixty human molars were assigned to six groups according to the adhesive systems (Adper Single Bond Plus and One Step Plus) and intraoral sites (incisor and molar sites). The room condition was used as a control group. Dentin fragments were individually placed in custom-made acetate trays and direct composite restorations were performed. The intraoral temperature and RH were recorded during adhesive procedures. Then, specimens were removed from the acetate trays and sectioned to obtain multiple beams for the microtensile bond strength test. In addition, the adhesive interface morphology was evaluated through scanning electron microscopy. Intraoral conditions were statistically analyzed by paired Students' t-tests and the bond strength data by two-way analysis of variance and Tukey test (α = 0.05). The posterior intraoral site showed a significant increase in the temperature and RH when compared with the anterior site. However, both intraoral sites revealed higher temperatures and RH than the room condition. In regards to the adhesive systems, the intraoral environment did not affect the bond strength, and the One Step Plus system showed the highest bond strength means. Despite the fact that remarkable changes in the intraoral conditions were observed for both anterior and posterior sites, the intraoral environment was not able to compromise the immediate dentin bond strength. Some conditions of intraoral temperature and relative humidity may not impair the dentin bond strength of two-step etch-and-rinse adhesive systems. Thus, an adequate relative isolation seems to be a good alternative under the specific clinical conditions in which rubber dam isolation is either impossible or very difficult to perform. © 2014 Wiley Periodicals, Inc.

Solid-state Bonding of Superplastic Aluminum Alloy 7475 Sheet

NASA Technical Reports Server (NTRS)

Byun, T. D. S.; Vastava, R. B.

1985-01-01

Experimental works were carried out to study the feasibility of solid state bonding of superplastic aluminum 7475 sheet. Amount of deformation, bonding time, surface cleaning method and intermediate layer were the process parameters investigated. Other parameters, held constant by the superplastic forming condition which is required to obtain a concurrent solid state bonding, are bonding temperature, bonding pressure and atmosphere. Bond integrity was evaluated through metallographic examination, X-ray line scan analysis, SEM fractographic analysis and lap shear tests. The early results of the development program indicated that sound solid state bonding was accomplished for this high strength 7475 alloy with significant amounts of deformation. A thin intermediate layer of the soft 5052 aluminum alloy aided in achieving a solid state bonding by reducing the required amount of plastic deformation at the interface. Bond strength was substantially increased by a post bond heat treatment.

Resin-dentin bond stability and physical characterization of a two-step self-etching adhesive system associated with TiF4.

PubMed

Torres, Gabriele Barbosa; da Silva, Tânia Mara; Basting, Rosanna Tarkany; Bridi, Enrico Coser; França, Fabiana Mantovani Gomes; Turssi, Cecilia Pedroso; do Amaral, Flávia Lucisano Botelho; de Paiva Gonçalves, Sérgio Eduardo; Basting, Roberta Tarkany

2017-10-01

To evaluate the bond strength to superficial (SD) and deep (DD) dentin after the use of 2.5% (T2.5%) or 4% (T4%) titanium tetrafluoride (TiF 4 ) in aqueous solution as a dentin pretreatment, or when incorporated into the primer (T2.5%P and T4%P) of an adhesive system (Clearfil SE Bond/CL). Degree of conversion (DC), particle size (PS), polydispersity index (PI) and zeta potential (ZP) of the solutions were evaluated. Fifty molars were sectioned longitudinally to obtain two slices of each tooth, which were demarcated into SD and DD. Treatments were applied (n=10): CL; T2.5%; T4%; T2.5%P; T4%P. After 24h or 180days storage, microshear bond strength tests were performed. The DC values of T2.5%P and T4%P were evaluated by FTIR. PS, PI and ZP were measured using dynamic light scattering. Analysis of mixed models showed significant effect of concentration of TiF 4 * solution * storage time (p=0.0075). There were higher bond strength values in SD than in DD (p=0.0105) for all treatments in both times. The failure mode showed adhesive failures in the majority of groups, irrespective of depth and time (p=0.3746). The bond strength values were not affected by treatments. Lower average particle size was observed for T2.5%P and T4%P at baseline. T2.5% and T4% showed a trend towards agglomeration. Higher bond strength values were achieved at SD for all treatments and times. The failure modes observed were adhesive. TiF 4 incorporation did not affect DC. T2.5%P and T4%P presented excellent stability over time. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The study of interaction between PFOA/PFOS and uracil by topology quality and spectroscopic analysis

NASA Astrophysics Data System (ADS)

Xu, Hui-Ying; Zhu, Jian-Qing; Wang, Wei; Xu, Xiao-Lu; Lu, Yin

2014-02-01

It has been established that perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) can be considered as emerging persistent organic pollutants. In recent years, there was increasing distribution of PFOA/PFOS in environmental systems, and accumulation and toxic effects of PFOA/PFOS in human body. In this paper, quantum chemistry methods were employed to study the interaction between perfluorinated organic pollutants and base (uracil). The results showed that there were four stable binding modes between the two perfluorinated compounds with uracil, especially the second mode which caused the most detrimental physiological functional response. NBO analysis showed that reactive hydrogen in the two perfluorinated compounds had the greatest effect on the hydrogen bond. The nature of the hydrogen bond formed between the two perfluorinated compounds and base was investigated using the AIM theory. The changes of spectroscopic properties in complexes were analyzed by IR and NMR spectra.

Corrosion Analysis of an Experimental Noble Alloy on Commercially Pure Titanium Dental Implants

PubMed Central

Bortagaray, Manuel Alberto; Ibañez, Claudio Arturo Antonio; Ibañez, Maria Constanza; Ibañez, Juan Carlos

2016-01-01

Objective: To determine whether the Noble Bond® Argen® alloy was electrochemically suitable for the manufacturing of prosthetic superstructures over commercially pure titanium (c.p. Ti) implants. Also, the electrolytic corrosion effects over three types of materials used on prosthetic suprastructures that were coupled with titanium implants were analysed: Noble Bond® (Argen®), Argelite 76sf +® (Argen®), and commercially pure titanium. Materials and Methods: 15 samples were studied, consisting in 1 abutment and one c.p. titanium implant each. They were divided into three groups, namely: Control group: five c.p Titanium abutments (B&W®), Test group 1: five Noble Bond® (Argen®) cast abutments and, Test group 2: five Argelite 76sf +® (Argen®) abutments. In order to observe the corrosion effects, the surface topography was imaged using a confocal microscope. Thus, three metric parameters (Sa: Arithmetical mean height of the surface. Sp: Maximum height of peaks. Sv: Maximum height of valleys.), were measured at three different areas: abutment neck, implant neck and implant body. The samples were immersed in artificial saliva for 3 months, after which the procedure was repeated. The metric parameters were compared by statistical analysis. Results: The analysis of the Sa at the level of the implant neck, abutment neck and implant body, showed no statistically significant differences on combining c.p. Ti implants with the three studied alloys. The Sp showed no statistically significant differences between the three alloys. The Sv showed no statistically significant differences between the three alloys. Conclusion: The effects of electrogalvanic corrosion on each of the materials used when they were in contact with c.p. Ti showed no statistically significant differences. PMID:27733875

The effect of a 980 nm diode laser with different parameters of irradiation on the bond strength of fiberglass posts.

PubMed

Garcia, Lucas da Fonseca Roberti; Naves, Lucas Zago; Farina, Ana Paula; Walker, Cristiane Mezzena; Consani, Simonides; Pires-de-Souza, Fernanda de Carvalho Panzeri

2011-01-01

The aim of this study was to assess bond strength of fiberglass posts to root canal dentin irradiated with a 980 nm diode laser at different parameters of power and frequency. Fifty human maxillary canines were separated into five groups (n = 10) according to the following parameters of laser power and frequency: Group 1 (1.5 W/100 Hz), Group 2 (1.5 W/continuous wave [CW]), Group 3 (3.0 W/100 Hz), Group 4 (3.0 W/CW), and Group 5 (no irradiation). Following post cementation, samples underwent a push-out test (0.5 mm/min); next, fracture analysis was performed with a light microscope at 50x and 100x magnification. All of the irradiated groups had increased bond strength values compared to the nonirradiated group. Groups 1 and 2 demonstrated the highest bond strength values; however, statistically significant differences were observed for only the cervical third of Group 4 and the cervical/apical thirds of Group 5. Fracture analysis showed a predominance of mixed failures for Groups 1 and 2 and adhesive failures between dentin and cement for the other groups.

A DFT-D Study on Structural, Electronic, Thermodynamic, and Mechanical Properties of HMX/MPNO Cocrystal under High Pressure

NASA Astrophysics Data System (ADS)

Lin, He; Chen, Jian-Fu; Cui, Yu-Ming; Zhang, Zhen-Jiang; Yang, Dong-Dong; Zhu, Shun-Guan; Li, Hong-Zhen

2017-04-01

An investigation on the structural, electronic, thermodynamic, and mechanical properties of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)/2-methylpyridine-N-oxide (MPNO) cocrystal was carried out from 0 to 100 GPa by using a dispersion-corrected density functional theory (DFT-D) method. Our calculated crystal structure is in excellent agreement with experimental results at ambient pressure. Based on the analysis of lattice parameters, lattice angles, bond lengths, bond angles, and dihedral angles under high pressure, we observe that HMX molecules in the cocrystal bulk are seriously distorted but MPNO molecules remain relatively unchanged. Hydrogen bond lengths are greatly shortened under high pressure. In addition, with the increase in pressure, the bandgap decreases gradually. However, it increases suddenly at 70 GPa. Some important hydrogen bonds between HMX and MPNO are also observed in the density of states spectrum. According to the thermodynamic analysis, this cocrystal is more easily prepared under low pressure. Finally, we characterized its mechanical properties and the results show that this cocrystal is malleable in nature. We expect that this research can provide a fundamental basis for further HMX cocrystal design and preparation.

Electronic Structure and Bonding in Complex Biomolecule

NASA Astrophysics Data System (ADS)

Ouyang, Lizhi

2005-03-01

For over a century vitamin B12 and its enzyme cofactor derivates have persistently attracted research efforts for their vital biological role, unique Co-C bonding, rich red-ox chemistry, and recently their candidacies as drug delivery vehicles etc. However, our understanding of this complex metalorganic molecule's efficient enzyme activated catalytic power is still controversial. We have for the first time calculated the electronic structure, Mulliken effective charge and bonding of a whole Vitamin B12 molecule without any structural simplification by first- principles approaches based on density functional theory using structures determined by high resolution X-ray diffraction. A partial density of states analysis shows excellent agreement with X-ray absorption data and has been used successfully to interpret measured optical absorption spectra. Mulliken bonding analysis of B12 and its derivatives reveal noticeable correlations between the two axial ligands which could be exploited by the enzyme to control the catalytic process. Our calculated X-ray near edge structure of B12 and its derivates using Slater's transition state theory are also in good agreement with experiments. The same approach has been applied to other B12 derivatives, ferrocene peptides, and recently DNA molecules.

Carbene-aerogen bonds: an ab initio study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Sabouri, Ayda

2017-04-01

Through the use of ab initio calculations, the possibility of formation of σ-hole interaction between ZO3 (Z = Ar, Kr and Xe) and carbene species is investigated. Since singlet carbenes show a negative electrostatic potential on their divalent carbon atom, they can favourably interact with the positive electrostatic potential generated by the σ-hole of Z atom of ZO3. The characteristic of this interaction, termed as 'carbene-aerogen' bond, is analysed in terms of geometric, interaction energies and electronic features. The energy decomposition analysis indicates that for all complexes analysed here, the electrostatic energy is more negative than the polarisation or dispersion energy term. According to the electron density analysis, some partial covalent character can be ascribed to XeṡṡṡC interactions. In addition, the carbene-aerogen bond exhibits cooperative effects with the HṡṡṡO hydrogen-bonding interaction in ternary complexes where both interactions coexist. For a given carbene, the amount of these cooperative effects increases with the size of the Z atom. The results obtained in this work may be helpful for the extension and future application of σ-hole intermolecular interactions as well as coordination chemistry.

Influence of Nd:YAG laser on the bond strength of self-etching and conventional adhesive systems to dental hard tissues.

PubMed

Marimoto, A K; Cunha, L A; Yui, K C K; Huhtala, M F R L; Barcellos, D C; Prakki, A; Gonçalves, S E P

2013-01-01

The aim of this study was to investigate the influence of Nd:YAG laser on the shear bond strength to enamel and dentin of total and self-etch adhesives when the laser was applied over the adhesives, before they were photopolymerized, in an attempt to create a new bonding layer by dentin-adhesive melting. One-hundred twenty bovine incisors were ground to obtain flat surfaces. Specimens were divided into two substrate groups (n=60): substrate E (enamel) and substrate D (dentin). Each substrate group was subdivided into four groups (n=15), according to the surface treatment accomplished: X (Xeno III self-etching adhesive, control), XL (Xeno III + laser Nd:YAG irradiation at 140 mJ/10 Hz for 60 seconds + photopolymerization, experimental), S (acid etching + Single Bond conventional adhesive, Control), and SL (acid etching + Single Bond + laser Nd:YAG at 140 mJ/10 Hz for 60 seconds + photopolymerization, experimental). The bonding area was delimited with 3-mm-diameter adhesive tape for the bonding procedures. Cylinders of composite were fabricated on the bonding area using a Teflon matrix. The teeth were stored in water at 37°C/48 h and submitted to shear testing at a crosshead speed of 0.5 mm/min in a universal testing machine. Results were analyzed with three-way analysis of variance (ANOVA; substrate, adhesive, and treatment) and Tukey tests (α=0.05). ANOVA revealed significant differences for the substrate, adhesive system, and type of treatment: lased or unlased (p<0.05). The mean shear bond strength values (MPa) for the enamel groups were X=20.2 ± 5.61, XL=23.6 ± 4.92, S=20.8 ± 4.55, SL=22.1 ± 5.14 and for the dentin groups were X=14.1 ± 7.51, XL=22.2 ± 6.45, S=11.2 ± 5.77, SL=15.9 ± 3.61. For dentin, Xeno III self-etch adhesive showed significantly higher shear bond strength compared with Single Bond total-etch adhesive; Nd:YAG laser irradiation showed significantly higher shear bond strength compared with control (unlased). Nd:YAG laser application prior to photopolymerization of adhesive systems significantly increased the bond strength to dentin.

Influence of the bracket on bonding and physical behavior of orthodontic resin cements.

PubMed

Bolaños-Carmona, Victoria; Zein, Bilal; Menéndez-Núñez, Mario; Sánchez-Sánchez, Purificación; Ceballos-García, Laura; González-López, Santiago

2015-01-01

The aim of the study is to determine the influence of the type of bracket, on bond strength, microhardness and conversion degree (CD) of four resin orthodontic cements. Micro-tensile bond strength (µTBS) test between the bracket base and the cement was carried out on glass-hour-shaped specimens (n=20). Vickers Hardness Number (VHN) and micro-Raman spectra were recorded in situ under the bracket base. Weibull distribution, ANOVA and non-parametric test were applied for data analysis (p<0.05). The highest values of ή as well as the β Weibull parameter were obtained for metallic brackets with Transbond™ plastic brackets with the self-curing cement showing the worst performance. The CD was from 80% to 62.5%.

Evidence for cis-trans isomerization of a double bond in the fatty acids of the psychrophilic bacterium Vibrio sp. strain ABE-1.

PubMed

Morita, N; Shibahara, A; Yamamoto, K; Shinkai, K; Kajimoto, G; Okuyama, H

1993-02-01

Vibrio sp. strain ABE-1 was grown in a medium that contained as its stable isotope tracer either [2,2-2H2]cis-9-hexadecenoic or [2,2-2H2]trans-9-hexadecenoic acid. Gas chromatographic-mass spectrometric analysis of the cis-9-hexadecenoic and trans-9-hexadecenoic acid fractions from the cells revealed the formation of an intracellularly isomerized 2,2-2H2-fatty acid which differed from the tracer only in the geometrical configuration of the double bond. This observation shows that cis-trans isomerization without a shift in double-bond position between these two geometric hexadecenoic acid isomers can occur in the cells.

Evidence for cis-trans isomerization of a double bond in the fatty acids of the psychrophilic bacterium Vibrio sp. strain ABE-1.

PubMed Central

Morita, N; Shibahara, A; Yamamoto, K; Shinkai, K; Kajimoto, G; Okuyama, H

1993-01-01

Vibrio sp. strain ABE-1 was grown in a medium that contained as its stable isotope tracer either [2,2-2H2]cis-9-hexadecenoic or [2,2-2H2]trans-9-hexadecenoic acid. Gas chromatographic-mass spectrometric analysis of the cis-9-hexadecenoic and trans-9-hexadecenoic acid fractions from the cells revealed the formation of an intracellularly isomerized 2,2-2H2-fatty acid which differed from the tracer only in the geometrical configuration of the double bond. This observation shows that cis-trans isomerization without a shift in double-bond position between these two geometric hexadecenoic acid isomers can occur in the cells. PMID:8423164

Shear Bond Strengths of Different Adhesive Systems to Biodentine

PubMed Central

Odabaş, Mesut Enes; Bani, Mehmet; Tirali, Resmiye Ebru

2013-01-01

The aim of this study was to measure the shear bond strength of different adhesive systems to Biodentine with different time intervals. Eighty specimens of Biodentine were prepared and divided into 8 groups. After 12 minutes, 40 samples were randomly selected and divided into 4 groups of 10 each: group 1: (etch-and-rinse adhesive system) Prime & Bond NT; group 2: (2-step self-etch adhesive system) Clearfil SE Bond; group 3: (1-step self-etch adhesive systems) Clearfil S3 Bond; group 4: control (no adhesive). After the application of adhesive systems, composite resin was applied over Biodentine. This procedure was repeated 24 hours after mixing additional 40 samples, respectively. Shear bond strengths were measured using a universal testing machine, and the data were subjected to 1-way analysis of variance and Scheffé post hoc test. No significant differences were found between all of the adhesive groups at the same time intervals (12 minutes and 24 hours) (P > .05). Among the two time intervals, the lowest value was obtained for group 1 (etch-and-rinse adhesive) at a 12-minute period, and the highest was obtained for group 2 (two-step self-etch adhesive) at a 24-hour period. The placement of composite resin used with self-etch adhesive systems over Biodentine showed better shear bond strength. PMID:24222742

Shear bond strengths of different adhesive systems to biodentine.

PubMed

Odabaş, Mesut Enes; Bani, Mehmet; Tirali, Resmiye Ebru

2013-01-01

The aim of this study was to measure the shear bond strength of different adhesive systems to Biodentine with different time intervals. Eighty specimens of Biodentine were prepared and divided into 8 groups. After 12 minutes, 40 samples were randomly selected and divided into 4 groups of 10 each: group 1: (etch-and-rinse adhesive system) Prime & Bond NT; group 2: (2-step self-etch adhesive system) Clearfil SE Bond; group 3: (1-step self-etch adhesive systems) Clearfil S(3) Bond; group 4: control (no adhesive). After the application of adhesive systems, composite resin was applied over Biodentine. This procedure was repeated 24 hours after mixing additional 40 samples, respectively. Shear bond strengths were measured using a universal testing machine, and the data were subjected to 1-way analysis of variance and Scheffé post hoc test. No significant differences were found between all of the adhesive groups at the same time intervals (12 minutes and 24 hours) (P > .05). Among the two time intervals, the lowest value was obtained for group 1 (etch-and-rinse adhesive) at a 12-minute period, and the highest was obtained for group 2 (two-step self-etch adhesive) at a 24-hour period. The placement of composite resin used with self-etch adhesive systems over Biodentine showed better shear bond strength.

The parental bonding in families of adolescents with anorexia: attachment representations between parents and offspring

PubMed Central

Balottin, Laura; Mannarini, Stefania; Rossi, Maura; Rossi, Giorgio; Balottin, Umberto

2017-01-01

Introduction The attachment theory is widely used in order to explain anorexia nervosa origin, course and treatment response. Nevertheless, very little literature specifically investigated parental bonding in adolescents with anorexia, as well as the parents’ own bonding and intergenerational transmission within the family. Purpose This study aims to identify any specific pattern of parental bonding in families of adolescents newly diagnosed with restricting-type anorexia, comparing them to the families of the control group. Patients and methods A total of 168 participants, adolescents and parents (78 belonging to the anorexia group and 90 to the control one), rated the perceived parental styles on the parental bonding instrument. The latent class analysis allowed the exploration of a maternal bonding latent variable and a paternal one. Results The main findings showed that a careless and overcontrolling parental style was recalled by the patients’ parents, and in particular by the fathers. As far as the adolescents’ responses were concerned, patients with anorexia did not seem to express differently their parental bonding perception from participants of the control group. Conclusion Clinical implications driven from the results suggest that a therapeutic intervention working on how the parents’ own attachment representations influence current relationships may help to modify the actual family functioning and thus the outcome of patients with anorexia. PMID:28203082

Effect of delayed polymerization time and bracket manipulation on orthodontic bracket bonding

NASA Astrophysics Data System (ADS)

Ponikvar, Michael J.

This study examined the effect of bracket manipulation in combination with delayed polymerization times on orthodontic bracket shear bond strength and degree of resin composite conversion. Orthodontics brackets were bonded to extracted third molars in a simulated oral environment after a set period of delayed polymerization time and bracket manipulation. After curing the bracket adhesive, each bracket underwent shear bond strength testing followed by micro-Raman spectroscopy analysis to measure the degree of conversion of the resin composite. Results demonstrated the shear bond strength and the degree of conversion of ceramic brackets did not vary over time. However, with stainless steel brackets there was a significant effect (p ≤ 0.05) of delay time on shear bond strength between the 0.5 min and 10 min bracket groups. In addition, stainless steel brackets showed significant differences related to degree of conversion over time between the 0.5 min and 5 min groups, in addition to the 0.5 min and 10 min groups. This investigation suggests that delaying bracket adhesive polymerization up to a period of 10 min then adjusting the orthodontic bracket may increase both shear bond strength and degree of conversion of stainless steel brackets while having no effect on ceramic brackets.

Effect of blood contamination on shear bond strength of orthodontic brackets and disinclusion buttons.

PubMed

Sfondrini, Maria Francesca; Gatti, Sara; Scribante, Andrea

2011-07-01

Our aim was to assess the effect of blood contamination on the shear bonding strength and sites of failure of orthodontic brackets and bondable buttons. We randomly divided 160 bovine permanent mandibular incisors into 8 groups of 20 specimens each. Both orthodontic brackets (Step brackets, Leone, Sesto Fiorentino, Italy) and bondable buttons (Flat orthodontic buttons, Leone, Sesto Fiorentino, Italy) were tested on four different enamel surfaces: dry; contamination with blood before priming; after priming; and before and after priming. Brackets and buttons were bonded to the teeth and subsequently tested using a Instron universal testing machine. Shear bonding strength and the rate of adhesive failures were recorded. Data were analysed using the analysis of variance (ANOVA), Scheffè tests, and the chi-square test. Uncontaminated enamel surfaces showed the highest bonding strengths for both brackets and buttons. When they were contaminated with blood, orthodontic brackets had significantly lower shear strengths than bondable buttons (P=0.0001). There were significant differences in sites of failure among the groups for the various enamel surfaces (P=0.001). Contamination of enamel by blood during bonding lowers the strength of the bond, more so with orthodontic brackets than with bondable buttons. Copyright © 2010 The British Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

Modulating of the pnicogen-bonding by a H⋯π interaction: An ab initio study.

PubMed

Esrafili, Mehdi D; Sadr-Mousavi, Asma

2017-08-01

An ab initio study of the cooperativity in XH 2 P⋯NCH⋯Z and XH 2 P⋯CNH⋯Z complexes (X=F, Cl, Br, CN, NC; Z=C 2 H 2 ,C 6 H 6 ) connected by pnicogen-bonding and H⋯π interactions is carried out by means of MP2 computational method. A detailed analysis of the structures, interaction energies and bonding properties is performed on these systems. For each set of the complexes considered, a favorable cooperativity is observed, especially in X=F and CN complexes. However, for a given X or Z, the amount of cooperativity effects in XH 2 P⋯CNH⋯Z complexes are more important than XH 2 P⋯NCH⋯Z counterparts. Besides, the influence of a H⋯π interaction on a P⋯N (C) bond is more pronounced than that of a P⋯N (C) bond on a H⋯π bond. The quantum theory of atoms in molecules shows that ternary complexes have increased electron densities at their bond critical points relative to the corresponding binary systems. The results also indicate that the strength of the P⋯N(C) and H⋯π interactions increases in the presence of the solvent. Copyright © 2017 Elsevier Inc. All rights reserved.

Hydrogen bonds in concreto and in computro: the sequel

NASA Astrophysics Data System (ADS)

Stouten, Pieter F. W.; Van Eijck, Bouke P.; Kroon, Jan

1991-02-01

In the framework of our comparative research concerning hydrogen bonding in the crystalline and liquid phases we have carried out molecular dynamics (MD) simulations of liquid methanol. Six different rigid three site models are compared. Five of them had been reported in the literature and one (OM2) we developed by a fit to the experimental molar volume, heat of vaporization and neutron weighted radial distribution function. In general the agreement with experiment is satisfactory for the different models. None of the models has an explicit hydrogen bond potential, but five of the six models show a degree of hydrogen bonding comparable to experiments on liquid methanol. The analysis of the simulation hydrogen bonds indicates that there is a distinct preference of the O⋯O axis to lie in the acceptor lone pairs plane, but hardly any for the lone pair directions. Ab initio calculations and crystal structure statistics of OH⋯O hydrogen bonds agree with this observation. The O⋯O hydrogen bond length distributions are similar for most models. The crystal structures show a sharper O⋯O distribution. Explicit introduction of harmonic motion with a quite realistic root mean square amplitude of 0.08 Å to the thermally averaged crystal distribution results in a distribution comparable to OM2 although the maximum of the former is found at shorter distance. On the basis of the analysis of the static properties of all models we conclude that our OM2, Jorgenson's OPLS and Haughney, Ferrario and McDonald's HFM1 models are good candidates for simulations of liquid methanol under isothermal, isochoric conditions. Partly flexible and completely rigid OM2 are simulated at constant pressure and with fixed volume. The flexible simulations give essentially the same (correct) results under both conditions, which is not surprising because the flexible form was fitted under both conditions. Rigid OM2 has a similar potential energy but larger pressure in the isochoric case and larger energy and far larger volume in the isobaric case. Radial distribution functions and hydrogen bond geometries are very similar for all four cases. Only in the case of the osobaric rigid methanol does the volume expansion seem to be accompanied by a slight preference for tetrahedrality around the oxygen atom.

The active site of hen egg-white lysozyme: flexibility and chemical bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Held, Jeanette, E-mail: jeanette.netzel@uni-bayreuth.de; Smaalen, Sander van

Chemical bonding at the active site of lysozyme is analyzed on the basis of a multipole model employing transferable multipole parameters from a database. Large B factors at low temperatures reflect frozen-in disorder, but therefore prevent a meaningful free refinement of multipole parameters. Chemical bonding at the active site of hen egg-white lysozyme (HEWL) is analyzed on the basis of Bader’s quantum theory of atoms in molecules [QTAIM; Bader (1994 ▶), Atoms in Molecules: A Quantum Theory. Oxford University Press] applied to electron-density maps derived from a multipole model. The observation is made that the atomic displacement parameters (ADPs) ofmore » HEWL at a temperature of 100 K are larger than ADPs in crystals of small biological molecules at 298 K. This feature shows that the ADPs in the cold crystals of HEWL reflect frozen-in disorder rather than thermal vibrations of the atoms. Directly generalizing the results of multipole studies on small-molecule crystals, the important consequence for electron-density analysis of protein crystals is that multipole parameters cannot be independently varied in a meaningful way in structure refinements. Instead, a multipole model for HEWL has been developed by refinement of atomic coordinates and ADPs against the X-ray diffraction data of Wang and coworkers [Wang et al. (2007), Acta Cryst. D63, 1254–1268], while multipole parameters were fixed to the values for transferable multipole parameters from the ELMAM2 database [Domagala et al. (2012), Acta Cryst. A68, 337–351] . Static and dynamic electron densities based on this multipole model are presented. Analysis of their topological properties according to the QTAIM shows that the covalent bonds possess similar properties to the covalent bonds of small molecules. Hydrogen bonds of intermediate strength are identified for the Glu35 and Asp52 residues, which are considered to be essential parts of the active site of HEWL. Furthermore, a series of weak C—H⋯O hydrogen bonds are identified by means of the existence of bond critical points (BCPs) in the multipole electron density. It is proposed that these weak interactions might be important for defining the tertiary structure and activity of HEWL. The deprotonated state of Glu35 prevents a distinction between the Phillips and Koshland mechanisms.« less

Effect of Fluoride and Simplified Adhesive Systems on the Bond Strength of Primary Molars and Incisors.

PubMed

Firoozmand, Leily Macedo; Noleto, Lawanne Ellen Carvalho; Gomes, Isabella Azevedo; Bauer, José Roberto de Oliveira; Ferreira, Meire Coelho

2015-01-01

The aim of this study was evaluate in vitro the influence of simplified adhesive systems (etch-and-rinse and self-etching) and 1.23% acidulated phosphate fluoride (APF) on the microshear bond strength (μ-SBS) of composite resins on primary molars and incisors. Forty primary molars and forty incisors vestibular enamel was treated with either the self-etching Clearfil SE Bond (CSE, Kuraray) or etch-and-rinse Adper Single Bond 2 (SB2, 3M/ESPE) adhesive system. Each group was subdivided based on the prior treatment of the enamel with or without the topical application of 1.23% APF. Thereafter, matrices were positioned and filled with composite resin and light cured. After storage in distilled water at 37 ± 1°C for 24 h, the specimens were submitted to μ-SBS in a universal testing machine. Kruskal-Wallis and Mann-Whitney tests (p < 0.05) showed that the prior application of 1.23% APF led to a significant reduction in bond strength. The type of adhesive exerted no significant influence bond strength. In the inter-group analysis, however, significantly bond strength reduction was found for the incisors when CSE was employed with APF. Adhesive failure was the most common type of fracture. The bond strength was affected by the prior application of 1.23% APF and type of tooth.

[Effects of magnetron sputtered ZrN on the bonding strength of titanium porcelain].

PubMed

Zhou, Shu; Zhang, Wen-yan; Guang, Han-bing; Xia, Yang; Zhang, Fei-min

2009-04-01

To investigate the effect of magnetron sputtered ZrN on the bonding strength between a low-fusing porcelain (Ti/Vita titankeramik system) and commercially pure cast titanium. Sixteen specimens were randomly assigned to test group and control group (n=8). The control group received no surface treated. Magnetron sputtered ZrN film was deposited on the surface of specimens in the test group. Then the sixteen titanium-porcelain specimens were prepared in a rectangular shape and went through three-point bending test on a universal test machine. The bond strength of Ti/porcelain was recorded. The phase composition of the specimens was analyzed using X-ray diffraction (XRD). The interface at titanium and porcelain and the titanium surface after debonding were observed with a scanning electron microscopy (SEM) and analyzed using energy depressive spectrum (EDS). New phase of ZrN was found with XRD in the test group. Statistical analysis showed higher bond strength following ZrN surface treatment in the test group [(45.991+/-0.648) MPa] than that in the control group [(29.483+/-1.007) MPa] (P=0.000). Bonded ceramic could be observed in test group, the amount of bonded ceramic was more than that in the control group. No obvious bonded ceramic in control group was found. Magnetron sputtered ZrN can improve bond strength of Ti/Vita titankeramik system significantly.

Quantitative assessment of intermolecular interactions by atomic force microscopy imaging using copper oxide tips

NASA Astrophysics Data System (ADS)

Mönig, Harry; Amirjalayer, Saeed; Timmer, Alexander; Hu, Zhixin; Liu, Lacheng; Díaz Arado, Oscar; Cnudde, Marvin; Strassert, Cristian Alejandro; Ji, Wei; Rohlfing, Michael; Fuchs, Harald

2018-05-01

Atomic force microscopy is an impressive tool with which to directly resolve the bonding structure of organic compounds1-5. The methodology usually involves chemical passivation of the probe-tip termination by attaching single molecules or atoms such as CO or Xe (refs 1,6-9). However, these probe particles are only weakly connected to the metallic apex, which results in considerable dynamic deflection. This probe particle deflection leads to pronounced image distortions, systematic overestimation of bond lengths, and in some cases even spurious bond-like contrast features, thus inhibiting reliable data interpretation8-12. Recently, an alternative approach to tip passivation has been used in which slightly indenting a tip into oxidized copper substrates and subsequent contrast analysis allows for the verification of an oxygen-terminated Cu tip13-15. Here we show that, due to the covalently bound configuration of the terminal oxygen atom, this copper oxide tip (CuOx tip) has a high structural stability, allowing not only a quantitative determination of individual bond lengths and access to bond order effects, but also reliable intermolecular bond characterization. In particular, by removing the previous limitations of flexible probe particles, we are able to provide conclusive experimental evidence for an unusual intermolecular N-Au-N three-centre bond. Furthermore, we demonstrate that CuOx tips allow the characterization of the strength and configuration of individual hydrogen bonds within a molecular assembly.

The Born-Oppenheimer molecular simulations of infrared spectra of crystalline poly-(R)-3-hydroxybutyrate with analysis of weak Csbnd H⋯Odbnd C hydrogen bonds

NASA Astrophysics Data System (ADS)

Brela, Mateusz Z.; Boczar, Marek; Wójcik, Marek J.; Sato, Harumi; Nakajima, Takahito; Ozaki, Yukihiro

2017-06-01

In this letter we present results of study of weak Csbnd H⋯Odbnd C hydrogen bonds of crystalline poly-(R)-3-hydroxybutyrate (PHB) by using Born-Oppenheimer molecular dynamics. The polymeric structure and IR spectra of PHB result from the presence of the weak hydrogen bonds. We applied the post-molecular dynamics analysis to consider a Cdbnd O motion as indirectly involved in the hydrogen bonds. Quantization of the nuclear motion of the oxygens was done to perform detailed analysis of the strength and properties of the Cdbnd O bands involved in the weak hydrogen bonds. We have also shown the dynamic character of the weak hydrogen bond interactions.

On the roles of close shell interactions in the structure of acyl-substituted hydrazones: An experimental and theoretical approach

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Ifzan Arshad, M.; Bolte, Michael; Fantoni, Adolfo C.; Delgado Espinoza, Zuly Y.; Erben, Mauricio F.

2016-03-01

The 2-(phenyl-hydrazono)-succinic acid dimethyl ester compound was synthesized by reacting phenylhydrazine with dimethylacetylene dicarboxylate at room temperature and characterized by elemental analysis, infrared, Raman, 1H and 13C NMR spectroscopies and mass spectrometry. Its solid state structure was determined by X-ray diffraction methods. The X-ray structure determination corroborates that the molecule is present in the crystal as the hydrazone tautomer, probably favored by a strong intramolecular N-H···Odbnd C hydrogen bond occurring between the carbonyl (-Cdbnd O) and the hydrazone -Cdbnd N-NH- groups. A substantial fragment of the molecular skeleton is planar due to an extended π-bonding delocalization. The topological analysis of the electron densities (Atom in Molecule, AIM) allows characterization of intramolecular N-H···O interaction, that can be classified as a resonant assisted hydrogen bond (RAHB). Moreover, the Natural Bond Orbital population analysis confirms that a strong hyperconjugative lpO1 → σ*(N2-H) remote interaction between the C2dbnd O1 and N2-H groups takes place. Periodic system electron density and topological analysis have been applied to characterize the intermolecular interactions in the crystal. Weak intermolecular interactions determine the crystal packing, and the prevalence of non-directional dispersive contributions are inferred on topological grounds. The IR spectrum of the crystalline compound was investigated by means of density functional theory calculations carried out with periodic boundary conditions on the crystal, showing excellent agreement between theory and the experiments. The vibrational assignment is complemented with the analysis of the Raman spectrum.

Stabilization of an immunoglobulin fold domain by an engineered disulfide bond at the buried hydrophobic region.

PubMed

Hagihara, Yoshihisa; Mine, Shouhei; Uegaki, Koichi

2007-12-14

We report for the first time the stabilization of an immunoglobulin fold domain by an engineered disulfide bond. In the llama single-domain antibody, which has human chorionic gonadotropin as its specific antigen, Ala49 and Ile70 are buried in the structure. A mutant with an artificial disulfide bond at this position showed a 10 degrees C higher midpoint temperature of thermal unfolding than that without the extra disulfide bond. The modified domains exhibited an antigen binding affinity comparable with that of the wild-type domain. Ala49 and Ile70 are conserved in camel and llama single-domain antibody frameworks. Therefore, domains against different antigens are expected to be stabilized by the engineered disulfide bond examined here. In addition to the effect of the loop constraints in the unfolded state, thermodynamic analysis indicated that internal interaction and hydration also control the stability of domains with disulfide bonds. The change in physical properties resulting from mutation often causes unpredictable and destabilizing effects on these interactions. The introduction of a hydrophobic cystine into the hydrophobic region maintains the hydrophobicity of the protein and is expected to minimize the unfavorable mutational effects.

Measurements of the Young's modulus of hydroxide catalysis bonds, and the effect on thermal noise in ground-based gravitational wave detectors

NASA Astrophysics Data System (ADS)

Phelps, Margot; van Veggel, Anna-Maria; Hough, James; Messenger, Chris; Hughes, David; Cunningham, William; Haughian, Karen; Rowan, Sheila

2018-05-01

With the outstanding results from the detection and observation of gravitational waves from coalescing black holes and neutron star inspirals, it is essential that pathways to further improve the sensitivities of the LIGO and VIRGO detectors are explored. There are a number of factors that potentially limit the sensitivities of the detectors. One such factor is thermal noise, a component of which results from the mechanical loss in the bond material between the silica fibre suspensions and the test mass mirrors. To calculate its magnitude, the Young's modulus of the bond material has to be known with reasonable accuracy. In this paper we present a new combination of ultrasonic technology and Bayesian analysis to measure the Young's modulus of hydroxide catalysis bonds between fused silica substrates. Using this novel technique, we measure the bond Young's modulus to be 18.5 ±2.32.0 GPa . We show that by applying this value to thermal noise models of bonded test masses with suitable attachment geometries, a reduction in suspension thermal noise consistent with an overall design sensitivity improvement allows a factor of 5 increase in event rate to be achieved.

Cooperativity of hydrogen-bonded networks in 7-azaindole(CH3OH)n (n=2,3) clusters evidenced by IR-UV ion-dip spectroscopy and natural bond orbital analysis.

PubMed

Sakota, Kenji; Kageura, Yutaka; Sekiya, Hiroshi

2008-08-07

IR-UV ion-dip spectra of the 7-azaindole (7AI)(CH(3)OH)(n) (n=1-3) clusters have been measured in the hydrogen-bonded NH and OH stretching regions to investigate the stable structures of 7AI(CH(3)OH)(n) (n=1-3) in the S(0) state and the cooperativity of the H-bonding interactions in the H-bonded networks. The comparison of the IR-UV ion-dip spectra with IR spectra obtained by quantum chemistry calculations shows that 7AI(CH(3)OH)(n) (n=1-3) have cyclic H-bonded structures, where the NH group and the heteroaromatic N atom of 7AI act as the proton donor and proton acceptor, respectively. The H-bonded OH stretch fundamental of 7AI(CH(3)OH)(2) is remarkably redshifted from the corresponding fundamental of (CH(3)OH)(2) by 286 cm(-1), which is an experimental manifestation of the cooperativity in H-bonding interaction. Similarly, two localized OH fundamentals of 7AI(CH(3)OH)(3) also exhibit large redshifts. The cooperativity of 7AI(CH(3)OH)(n) (n=2,3) is successfully explained by the donor-acceptor electron delocalization interactions between the lone-pair orbital in the proton acceptor and the antibonding orbital in the proton donor in natural bond orbital (NBO) analyses.

Role of dispersion corrected hybrid GGA class in accurately calculating the bond dissociation energy of carbon halogen bond: A benchmark study

NASA Astrophysics Data System (ADS)

Kosar, Naveen; Mahmood, Tariq; Ayub, Khurshid

2017-12-01

Benchmark study has been carried out to find a cost effective and accurate method for bond dissociation energy (BDE) of carbon halogen (Csbnd X) bond. BDE of C-X bond plays a vital role in chemical reactions, particularly for kinetic barrier and thermochemistry etc. The compounds (1-16, Fig. 1) with Csbnd X bond used for current benchmark study are important reactants in organic, inorganic and bioorganic chemistry. Experimental data of Csbnd X bond dissociation energy is compared with theoretical results. The statistical analysis tools such as root mean square deviation (RMSD), standard deviation (SD), Pearson's correlation (R) and mean absolute error (MAE) are used for comparison. Overall, thirty-one density functionals from eight different classes of density functional theory (DFT) along with Pople and Dunning basis sets are evaluated. Among different classes of DFT, the dispersion corrected range separated hybrid GGA class along with 6-31G(d), 6-311G(d), aug-cc-pVDZ and aug-cc-pVTZ basis sets performed best for bond dissociation energy calculation of C-X bond. ωB97XD show the best performance with less deviations (RMSD, SD), mean absolute error (MAE) and a significant Pearson's correlation (R) when compared to experimental data. ωB97XD along with Pople basis set 6-311g(d) has RMSD, SD, R and MAE of 3.14 kcal mol-1, 3.05 kcal mol-1, 0.97 and -1.07 kcal mol-1, respectively.

[Preliminary study of bonding strength between diatomite-based dental ceramic and veneering porcelains].

PubMed

Lu, Xiao-li; Gao, Mei-qin; Cheng, Yu-ye; Zhang, Fei-min

2015-04-01

In order to choose the best veneering porcelain for diatomite-based dental ceramic substrate, the bonding strength between diatomite-based dental ceramics and veneering porcelains was measured, and the microstructure and elements distribution of interface were analyzed. The coefficient of thermal expansion (CTE) of diatomite-based dental ceramics was detected by dilatometry. Three veneering porcelain materials were selected with the best CTE matching including alumina veneering porcelain (group A), titanium porcelain veneering porcelain (group B), and E-max veneering porcelain (group C). Shear bonding strength was detected. SEM and EDS were used to observe the interface microstructure and element distribution. Statistical analysis was performed using SPSS 17.0 software package. The CTE of diatomite-based dental ceramics at 25-500 degrees centigrade was 8.85×10-6K-1. The diatomite-based substrate ceramics combined best with group C. Shear bonding strength between group A and C and group B and C both showed significant differences(P<0.05). SEM and EDS showed that the interface of group C sintered tightly and elements permeated on both sides of the interface. The diatomite-based substrate ceramics combines better with E-max porcelain veneer.

HBonanza: A Computer Algorithm for Molecular-Dynamics-Trajectory Hydrogen-Bond Analysis

PubMed Central

Durrant, Jacob D.; McCammon, J. Andrew

2011-01-01

In the current work, we present a hydrogen-bond analysis of 2,673 ligand-receptor complexes that suggests the total number of hydrogen bonds formed between a ligand and its protein receptor is a poor predictor of ligand potency; furthermore, even that poor prediction does not suggest a statistically significant correlation between hydrogen-bond formation and potency. While we are not the first to suggest that hydrogen bonds on average do not generally contribute to ligand binding affinities, this additional evidence is nevertheless interesting. The primary role of hydrogen bonds may instead be to ensure specificity, to correctly position the ligand within the active site, and to hold the protein active site in a ligand-friendly conformation. We also present a new computer program called HBonanza (hydrogen-bond analyzer) that aids the analysis and visualization of hydrogen-bond networks. HBonanza, which can be used to analyze single structures or the many structures of a molecular dynamics trajectory, is open source and python implemented, making it easily editable, customizable, and platform independent. Unlike many other freely available hydrogen-bond analysis tools, HBonanza provides not only a text-based table describing the hydrogen-bond network, but also a Tcl script to facilitate visualization in VMD, a popular molecular visualization program. Visualization in other programs is also possible. A copy of HBonanza can be obtained free of charge from http://www.nbcr.net/hbonanza. PMID:21880522

Micromorphological characterization of adhesive interface of sound dentin and total-etch and self-etch adhesives.

PubMed

Drobac, Milan; Stojanac, Igor; Ramić, Bojana; Premović, Milica; Petrović, Ljubomir

2015-01-01

The ultimate goal in restorative dentistry has always been to achieve strong and permanent bond between the dental tissues and filling materials. It is not easy to achieve this task because the bonding process is different for enamel and dentin-dentin is more humid and more organic than enamel. It is moisture and organic nature of dentin that make this hard tissue very complex to achieve adhesive bond. One of the first and most widely used tools for examining the adhesive bond between hard dental tissues and composite restorative materials is scanning electron microscopy. The aim of this study was scanning electron microscopy analyzes the interfacial micro morphology of total-etch and self-etch adhesives. Micro morphological characteristics of interface between total-etch adhesive (Prime & Bond NT) in combination with the corresponding composite (Ceram X Mono) were compared with those of self-etching adhesive (AdheSE One) in, combination with the corresponding composite (Tetric EvoCeram). The specimens were observed under 1000 x magnification of scanning electron microscopy (JEOL, JSM-6460 Low Vacuum). Measurement of the thickness of the hybrid layer of the examined com posite systems was performed with the software of the device used (NIH Image Analyser). Micromorphological analysis of interface showed that the hybrid layer in sound dentin was well formed, its average thickness being 2.68 microm, with a large number of resin tags and a large amount of lateral branches for specimens with a composite system Prime & Bond NT-Ceram X Mono. However, the specimens' with composite systems Adhese One-Tetric EvoCeram did not show the presence of hybrid layer and the resin tags were poorly represented. The results of this study suggest that total-etch adhesives bond better with sound dentin than self-etch adhesive.

Evaluation of Microtensile Bond Strength and Microleakage of a Self-adhering Flowable Composite.

PubMed

Yuan, He; Li, Mingyang; Guo, Bin; Gao, Yuan; Liu, HongLing; Li, Jiyao

2015-12-01

To evaluate the microtensile bond strength (μTBS) and marginal sealing ability of a self-adhering flowable composite between dentin and composite interfaces, as well as the microleakage of Class V restorations. The occlusal thirds of 40 third molars were removed and randomly divided into 4 groups according to the applied adhesive: Adper Easy One (AEO, 3M ESPE), Clearfil SE Bond (CSEB, Kuraray), Prime & Bond NT (PBNT, Dentsply) and a self-adhering flowable composite (Dyad Flow, DF, Kerr). Filtek Flowable (3M ESPE) resin composite crowns were then built up in the first three groups; in group DF, composite crowns were built up without the application of an adhesive. Thirty stick-shaped microspecimens were prepared per group, 10 of which were used for morphological observation of bonded interfaces by scanning electron microscopy (SEM) after decalcification. The remaining microspecimens underwent microtensile bond strength testing and the failure mode was analyzed. Microleakage evaluation was performed on 10 premolars per group in which standardized box-shaped Class V cavities were prepared. After 500 thermocycles, the premolars were immersed in 1% methylene blue for 24 h, and three slices from each tooth were observed under a stereomicroscope and scored. Statistical analysis was performed using one-way ANOVA, Student-Newman-Keuls and chi-square tests. The PBNT group presented the highest μTBS values, followed by the CSEB and AEO groups, which did not differ significantly from each other. The DF group showed the lowest μTBS values. No significant differences in microleakage were observed among these four groups. Although individual usage of the self-adhering flowable composite showed the lowest bond strength, the same marginal sealing ability was observed as that of combining self-etching and etch-and-rinse adhesives with flowable composite.

On the nature of interactions in the F2 OXe(…) NCCH3 complex: Is there the Xe(IV)N bond?

PubMed

Makarewicz, Emilia; Lundell, Jan; Gordon, Agnieszka J; Berski, Slawomir

2016-07-01

Nature of the bonding in isolated XeOF2 molecule and F2 OXe(…) NCCH3 complexes have been studied in the gas phase (0 K) using Quantum Chemical Topology methods. The wave functions have been approximated at the MP2 and DFT levels of calculations, using the APFD, B3LYP, M062X, and B2PLYP functionals with the GD3 dispersion correction. The nature of the formal XeO bond in the XeOF2 monomer depends on the basis set used (all-electron vs. the ecp-28 approximation for Xe). Within the all-electron basis set approach the bond is represented by two bonding attractors, Vi = 1,2 (Xe,O), with total population of about 1.06e and highly delocalized electron density in both bonding basins. No bonding basins are observed using the ecp-28 approximation. These results shows that the nature of xenon-oxygen is complicated and may be described with mesomeric equilibrium of the Lewis representations: Xe((+)) O((-)) and Xe((-)) O((+)) . For both the xenon-oxygen and xenon-fluorine interactions the charge-shift model can be applied. The F2 OXe(…) NCCH3 complex exists in two structures: "parallel," stabilized by non-covalent C(…) O and Xe(…) N interactions and "linear" stabilized by the Xe(…) N interaction. Topological analysis of ELF shows that the F2 OXe(…) NCCH3 molecule appears as a weakly bound intermolecular complex. Intermolecular interaction energy components have also been studied using Symmetry Adapted Perturbation Theory. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Effect of Er:YAG Laser and Sandblasting in Recycling of Ceramic Brackets.

PubMed

Yassaei, Soghra; Aghili, Hossein; Hosseinzadeh Firouzabadi, Azadeh; Meshkani, Hamidreza

2017-01-01

Introduction: This study was performed to determine the shear bond strength of rebonded mechanically retentive ceramic brackets after recycling with Erbium-Doped Yttrium Aluminum Garnet (Er:YAG) laser or sandblasting. Methods: Twenty-eight debonded ceramic brackets plus 14 intact new ceramic brackets were used in this study. Debonded brackets were randomly divided into 2 groups of 14. One group was treated by Er:YAG laser and the other with sandblasting. All the specimens were randomly bonded to 42 intact human upper premolars. The shear bond strength of all specimens was determined with a universal testing machine at a crosshead speed of 0.5 mm/min until bond failure occurred. The recycled bracket base surfaces were observed under a scanning electron microscope (SEM). Analysis of variance (ANOVA) and Tukey tests were used to compare the shear bond strength of the 3 groups. Fisher exact test was used to evaluate the differences in adhesive remnant index (ARI) scores. Results: The highest bond strength belonged to brackets recycled by Sandblasting (16.83 MPa). There was no significant difference between the shear bond strength of laser and control groups. SEM photographs showed differences in 2 recycling methods. The laser recycled bracket appeared to have as well-cleaned base as the new bracket. Although the sandblasted bracket photographs showed no remnant adhesives, remarkable micro-roughening of the base of the bracket was apparent. Conclusion: According to the results of this study, both Er:YAG laser and sandblasting were efficient to mechanically recondition retentive ceramic brackets. Also, Er:YAG laser did not change the design of bracket base while removing the remnant adhesives which might encourage its application in clinical practice.

Effect of Er:YAG Laser and Sandblasting in Recycling of Ceramic Brackets

PubMed Central

Yassaei, Soghra; Aghili, Hossein; Hosseinzadeh Firouzabadi, Azadeh; Meshkani, Hamidreza

2017-01-01

Introduction: This study was performed to determine the shear bond strength of rebonded mechanically retentive ceramic brackets after recycling with Erbium-Doped Yttrium Aluminum Garnet (Er:YAG) laser or sandblasting. Methods: Twenty-eight debonded ceramic brackets plus 14 intact new ceramic brackets were used in this study. Debonded brackets were randomly divided into 2 groups of 14. One group was treated by Er:YAG laser and the other with sandblasting. All the specimens were randomly bonded to 42 intact human upper premolars. The shear bond strength of all specimens was determined with a universal testing machine at a crosshead speed of 0.5 mm/min until bond failure occurred. The recycled bracket base surfaces were observed under a scanning electron microscope (SEM). Analysis of variance (ANOVA) and Tukey tests were used to compare the shear bond strength of the 3 groups. Fisher exact test was used to evaluate the differences in adhesive remnant index (ARI) scores. Results: The highest bond strength belonged to brackets recycled by Sandblasting (16.83 MPa). There was no significant difference between the shear bond strength of laser and control groups. SEM photographs showed differences in 2 recycling methods. The laser recycled bracket appeared to have as well-cleaned base as the new bracket. Although the sandblasted bracket photographs showed no remnant adhesives, remarkable micro-roughening of the base of the bracket was apparent. Conclusion: According to the results of this study, both Er:YAG laser and sandblasting were efficient to mechanically recondition retentive ceramic brackets. Also, Er:YAG laser did not change the design of bracket base while removing the remnant adhesives which might encourage its application in clinical practice. PMID:28912939

Effect of double-layer application on dentin bond durability of one-step self-etch adhesives.

PubMed

Taschner, M; Kümmerling, M; Lohbauer, U; Breschi, L; Petschelt, A; Frankenberger, R

2014-01-01

The aim of this in vitro study was 1) to analyze the influence of a double-layer application technique of four one-step self-etch adhesive systems on dentin and 2) to determine its effect on the stability of the adhesive interfaces stored under different conditions. Four different one-step self-etch adhesives were selected for the study (iBondSE, Clearfil S(3) Bond, XenoV(+), and Scotchbond Universal). Adhesives were applied according to manufacturers' instructions or with a double-layer application technique (without light curing of the first layer). After bonding, resin-dentin specimens were sectioned for microtensile bond strength testing in accordance with the nontrimming technique and divided into 3 subgroups of storage: a) 24 hours (immediate bond strength, T0), b) six months (T6) in artificial saliva at 37°C, or c) five hours in 10 % NaOCl at room temperature. After storage, specimens were stressed to failure. Fracture mode was assessed under a light microscope. At T0, iBond SE showed a significant increase in microtensile bond strength when the double-application technique was applied. All adhesive systems showed reduced bond strengths after six months of storage in artificial saliva and after storage in 10% NaOCl for five hours; however at T6, iBond SE, Clearfil S(3) Bond, and XenoV(+) showed significantly higher microtensile bond strength results for the double-application technique compared with the single-application technique. Scotchbond Universal showed no difference between single- or double-application, irrespective of the storage conditions. The results of this study show that improvements in bond strength of one-step self-etch adhesives by using the double-application technique are adhesive dependent.

An equivalent dipole analysis of PZT ceramics and lead-free piezoelectric single crystals

NASA Astrophysics Data System (ADS)

Bell, Andrew J.

2016-04-01

The recently proposed Equivalent Dipole Model for describing the electromechanical properties of ionic solids in terms of 3 ions and 2 bonds has been applied to PZT ceramics and lead-free single crystal piezoelectric materials, providing analysis in terms of an effective ionic charge and the asymmetry of the interatomic force constants. For PZT it is shown that, as a function of composition across the morphotropic phase boundary, the dominant bond compliance peaks at 52% ZrO2. The stiffer of the two bonds shows little composition dependence with no anomaly at the phase boundary. The effective charge has a maximum value at 50% ZrO2, decreasing across the phase boundary region, but becoming constant in the rhombohedral phase. The single crystals confirm that both the asymmetry in the force constants and the magnitude of effective charge are equally important in determining the values of the piezoelectric charge coefficient and the electromechanical coupling coefficient. Both are apparently temperature dependent, increasing markedly on approaching the Curie temperature.

Investigation of the gas-phase structure and rotational barrier of trimethylsilyl trifluoromethanesulfonate and comparison with covalent sulfonates

NASA Astrophysics Data System (ADS)

Defonsi Lestard, María E.; Tuttolomondo, María E.; Varetti, Eduardo L.; Wann, Derek A.; Robertson, Heather E.; Rankin, David W. H.; Altabef, Aida Ben

2010-12-01

The molecular structure of trimethylsilyl trifluoromethanesulfonate, CF 3SO 2OSi(CH 3) 3, has been determined in the gas phase from electron-diffraction data supplemented by ab initio (MP2) and DFT calculations using 6-31G(d), 6-311++G(d,p) and 6-311G++(3df,3pd) basis sets. Both experimental and theoretical data indicate that only one gauche conformer is possible by rotating about the O-S bond. The anomeric effect is a fundamental stereoelectronic interaction and presents a profound influence on the electronic geometry. We have investigated the origin of the anomeric effect by means of NBO and AIM analysis. A natural bond orbital analysis showed that the lpπ[O bonded to Si)] → σ *[C-S] hyperconjugative interaction favors the gauche conformation. In addition, comparison of the structural and stereoelectronic properties of the title molecule with those of silyl trifluoromethanesulfonate and methyl trifluoromethanesulfonate has been carried out.

Structural and computational analysis of intermolecular interactions in a new 2-thiouracil polymorph.

PubMed

Fabijanić, Ivana; Matković-Čalogović, Dubravka; Pilepić, Viktor; Sanković, Krešimir

2017-12-01

The crystallization and characterization of a new polymorph of 2-thiouracil by single-crystal X-ray diffraction, Hirshfeld surface analysis and periodic density functional theory (DFT) calculations are described. The previously published polymorph (A) crystallizes in the triclinic space group P\\overline{1}, while that described herein (B) crystallizes in the monoclinic space group P2 1 /c. Periodic DFT calculations showed that the energies of polymorphs A and B, compared to the gas-phase geometry, were -108.8 and -29.4 kJ mol -1 , respectively. The two polymorphs have different intermolecular contacts that were analyzed and are discussed in detail. Significant differences in the molecular structure were found only in the bond lengths and angles involving heteroatoms that are involved in hydrogen bonds. Decomposition of the Hirshfeld fingerprint plots revealed that O...H and S...H contacts cover over 50% of the noncovalent contacts in both of the polymorphs; however, they are quite different in strength. Hydrogen bonds of the N-H...O and N-H...S types were found in polymorph A, whereas in polymorph B, only those of the N-H...O type are present, resulting in a different packing in the unit cell. QTAIM (quantum theory of atoms in molecules) computational analysis showed that the interaction energies for these weak-to-medium strength hydrogen bonds with a noncovalent or mixed interaction character were estimated to fall within the ranges 5.4-10.2 and 4.9-9.2 kJ mol -1 for polymorphs A and B, respectively. Also, the NCI (noncovalent interaction) plots revealed weak stacking interactions. The interaction energies for these interactions were in the ranges 3.5-4.1 and 3.1-5.5 kJ mol -1 for polymorphs A and B, respectively, as shown by QTAIM analysis.

The natural food colorant Peonidin from cranberries as a potential radical scavenger - A DFT based mechanistic analysis.

PubMed

Rajan, Vijisha K; Hasna, C K; Muraleedharan, K

2018-10-01

A theoretical evaluation of the antioxidant property of a natural food colorant Peonidin has been performed. The most suitable mechanism for explaining the radical scavenging capacity of Peonidin is the Hydrogen Atom Transfer and the most active site for radical formation is position 3 and is confirmed through Mulliken charge analysis, pKa value evaluation, Bond Dissociation Energy values, and Natural Bond Orbital analysis. Position 3 and 5 in Peonidin exists in blood as deprotonated as their pKa values are lower than the pH of blood. Peonidin is highly reactive than Quercetin and less stable than flavan-3-ols due to the small band gap. Global descriptor analysis shows that PN prefers to accept electrons than to donate. The effect of number of OH groups and the nature of substituents are well explained through this work. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydrogen bonding in water clusters and their ionized counterparts.

PubMed

Neela, Y Indra; Mahadevi, A Subha; Sastry, G Narahari

2010-12-30

Ab initio and DFT computations were carried out on four distinct hydrogen-bonded arrangements of water clusters (H(2)O)(n), n = 2-20, represented as W1D, W2D, W2DH, and W3D. The variation in the strength of hydrogen bond as a function of the chain length is studied. In all the four cases, there is a substantial cooperative interaction, albeit in different degrees. The effect of basis set superposition error (BSSE) on the complexation energy of water clusters has been analyzed. Atoms in molecules (AIM) analysis performed to evaluate the nature of the hydrogen bonding shows a high correlation between hydrogen bond strength and the trends in complexation energy. Solvated water clusters exhibit lower complexation energies compared to corresponding gas-phase geometries on PCM (polarized continuum model) optimization. The feasibility of stripping an electron or addition of an electron increases dramatically as the cluster size increases. Although W3D caged structures are stable for neutral clusters, the helical W2DH arrangement appeared to be an optimal choice for its ionized counterparts.

Formation and Characterization of Silver Nanoparticle Composite with Poly(p-Br/F-phenylsilane).

PubMed

Roh, Sung-Hee; Noh, Ji Eun; Woo, Hee-Gweon; Cho, Myong-Shik; Sohn, Honglae

2015-02-01

The one-pot production and structural characterization of composites of silver nanoparticles with poly(p-Br/F-phenylsilane), Br/F-PPS, have been performed. The conversion of Ag+ ions to stable Ag0 nanoparticles is mediated by the copolymer Br/F-PPS having both possibly reactive Si-H bonds in the polymer backbone and C-Br bonds in the substituents along with relatively inert C-F bonds. Transmission electron microscopy and field emission scanning electron microscopy analyses show the formation of the composites where silver nanoparticles (less than 30 nm of size) are well dispersed over the Br/F-PPS matrix. X-ray diffraction patterns are consistent with that for face-centered-cubic typed silver. The polymer solubility in toluene implys that the cleavage of C-Br bond and the Si-F dative bonding may not be occurred appreciably at ambient temperature. Nonetheless, thermogravimetric analysis data suggest that some sort of cross-linking could take place at high temperature. Most of the silver particles undergo macroscopic aggregation without Br/F-PPS, which indicates that the polysilane is necessary for stabilizing the silver nanoparticles.

Automated optical inspection of liquid crystal display anisotropic conductive film bonding

NASA Astrophysics Data System (ADS)

Ni, Guangming; Du, Xiaohui; Liu, Lin; Zhang, Jing; Liu, Juanxiu; Liu, Yong

2016-10-01

Anisotropic conductive film (ACF) bonding is widely used in the liquid crystal display (LCD) industry. It implements circuit connection between screens and flexible printed circuits or integrated circuits. Conductive microspheres in ACF are key factors that influence LCD quality, because the conductive microspheres' quantity and shape deformation rate affect the interconnection resistance. Although this issue has been studied extensively by prior work, quick and accurate methods to inspect the quality of ACF bonding are still missing in the actual production process. We propose a method to inspect ACF bonding effectively by using automated optical inspection. The method has three steps. The first step is that it acquires images of the detection zones using a differential interference contrast (DIC) imaging system. The second step is that it identifies the conductive microspheres and their shape deformation rate using quantitative analysis of the characteristics of the DIC images. The final step is that it inspects ACF bonding using a back propagation trained neural network. The result shows that the miss rate is lower than 0.1%, and the false inspection rate is lower than 0.05%.

Bond efficacy of recycled orthodontic brackets: A comparative in vitro evaluation of two methods.

PubMed

Shetty, Vikram; Shekatkar, Yash; Kumbhat, Neesu; Gautam, G; Karbelkar, Shalan; Vandekar, Meghna

2015-01-01

Recycling of orthodontic brackets in developing orthodontic economies is an extremely common procedure. Bonding protocols and reliability of these brackets is, however, questionable, and still the subject of research. The aim was to evaluate and compare the shear bond strength of brackets recycled with sandblasting and silicoating. Ninety extracted human premolars were bonded with 0.022" SS brackets (American Orthodontics, Sheboygan USA) and then debonded. The debonded brackets were divided into three groups of 30 each. Group I: Sandblasting with 50-μm aluminum oxide (control group) Group II: Sandblasting with 50-μm aluminum oxide followed by metal primer application Group III: Silicoating with 30-μm Cojet sand followed by silane application and rebonded with Transbond XT. The sandblasted brackets and silicoated brackets were viewed under the scanning electron microscope, immediately after surface conditioning before rebonding. The shear bond strength with each group was tested. One-way analysis of variance, post-hoc Scheffe multiple comparison tests. The results showed that sandblasting created more irregularities and deeper erosions while silica coating created superficial irregularities and shallow erosions.

Ultra-stiff metallic glasses through bond energy density design.

PubMed

Schnabel, Volker; Köhler, Mathias; Music, Denis; Bednarcik, Jozef; Clegg, William J; Raabe, Dierk; Schneider, Jochen M

2017-07-05

The elastic properties of crystalline metals scale with their valence electron density. Similar observations have been made for metallic glasses. However, for metallic glasses where covalent bonding predominates, such as metalloid metallic glasses, this relationship appears to break down. At present, the reasons for this are not understood. Using high energy x-ray diffraction analysis of melt spun and thin film metallic glasses combined with density functional theory based molecular dynamics simulations, we show that the physical origin of the ultrahigh stiffness in both metalloid and non-metalloid metallic glasses is best understood in terms of the bond energy density. Using the bond energy density as novel materials design criterion for ultra-stiff metallic glasses, we are able to predict a Co 33.0 Ta 3.5 B 63.5 short range ordered material by density functional theory based molecular dynamics simulations with a high bond energy density of 0.94 eV Å -3 and a bulk modulus of 263 GPa, which is 17% greater than the stiffest Co-B based metallic glasses reported in literature.

Pressure-Induced Amorphization in Single-Crystal Ta2O5 Nanowires: A Kinetic Mechanism and Improved Electrical Conductivity

NASA Astrophysics Data System (ADS)

Lu, Xujie; Hu, Qingyang; Yang, Wenge; Bai, Ligang; Sheng, Howard; Wang, Lin; Huang, Fuqiang; Wen, Jianguo; Miller, Dean; Zhao, Yusheng

2014-03-01

Pressure-induced amorphization (PIA) in single-crystal Ta2O5 nanowires is observed at 19 GPa and the obtained amorphous Ta2O5 nanowires show significant improvement in electrical conductivity. The phase transition process is unveiled by monitoring structural evolution with in-situ synchrotron XRD, PDF, Raman spectroscopy and TEM. The first principles calculations reveal the phonon modes softening during compression at particular bonds, and the analysis on the electron localization function also shows bond strength weakening at the same positions. Based on the experimental and theoretical results, a kinetic PIA mechanism is proposed and demonstrated systematically that amorphization is initiated by the disruption of connectivity between polyhedra at the particular weak-bonding positions along the a-axis in the unit cell. The one-dimensional morphology is well preserved for the pressure-induced amorphous Ta2O5 and the electrical conductivity is improved by an order of magnitude compared to traditional amorphous forms.

Folding of a helix is critically stabilized by polarization of backbone hydrogen bonds: study in explicit water.

PubMed

Duan, Li L; Gao, Ya; Mei, Ye; Zhang, Qing G; Tang, Bo; Zhang, John Z H

2012-03-15

Multiple single-trajectory molecular dynamics (MD) simulation at room temperature (300 K) in explicit water was carried out to study the folding dynamics of an α-helix (PDB 2I9M ) using a polarized charge scheme that includes electronic polarization of backbone hydrogen bonds. Starting from an extended conformation, the 17-residue peptide was successfully folded into the native structure (α-helix) between 80 and 130 ns with a root-mean-square deviation of ~1.0 Å. Analysis of the time-dependent trajectories revealed that helix formation of the peptide started at the terminals and progressed toward the center of the peptide. For comparison, MD trajectories generated under various versions of standard AMBER force fields failed to show any significant or stable helix formation in our simulation. Our result shows clear evidence that the electronic polarization of backbone hydrogen bonds energetically stabilizes the helix formation and is critical to the stable folding of the short helix structure. © 2012 American Chemical Society

Bisphenol A release from orthodontic adhesives measured in vitro and in vivo with gas chromatography.

PubMed

Moreira, Marília Rodrigues; Matos, Leonardo Gontijo; de Souza, Israel Donizeti; Brigante, Tamires Amabile Valim; Queiroz, Maria Eugênia Costa; Romano, Fábio Lourenço; Nelson-Filho, Paulo; Matsumoto, Mírian Aiko Nakane

2017-03-01

The objectives of this study were to quantify in vitro the Bisphenol A (BPA) release from 5 orthodontic composites and to assess in vivo the BPA level in patients' saliva and urine after bracket bonding with an orthodontic adhesive system. For the in-vitro portion of this study, 5 orthodontic composites were evaluated: Eagle Spectrum (American Orthodontics, Sheboygan, Wis), Enlight (Ormco, Orange, Calif), Light Bond (Reliance Orthodontic Products, Itasca, Ill), Mono Lok II (Rocky Mountain Orthodontics, Denver, Colo), and Transbond XT (3M Unitek, Monrovia, Calif). Simulating intraoral conditions, the specimens were immersed in a water/ethanol solution, and the BPA (ng.g -1 ) liberation was measured after 30 minutes, 24 hours, 1 day, 1 week, and 1 month by the gas chromatography system coupled with mass spectrometry. Twenty patients indicated for fixed orthodontic treatment participated in the in-vivo study. Saliva samples were collected before bracket bonding and then 30 minutes, 24 hours, 1 day, 1 week, and 1 month after bonding the brackets. Urine samples were collected before bonding and then at 1 day, 1 week, and 1 month after bonding. The results were analyzed statistically using analysis of variance and Tukey posttest, with a significance level of 5%. All composites evaluated in vitro released small amounts of BPA. Enlight composite showed the greatest release, at 1 month. Regarding the in-vivo study, the mean BPA level in saliva increased significantly only at 30 minutes after bonding in comparison with measurements recorded before bonding. All orthodontic composites released BPA in vitro. Enlight and Light Bond had, respectively, the highest and lowest BPA releases in vitro. The in-vivo experiment showed that bracket bonding with the Transbond XT orthodontic adhesive system resulted in increased BPA levels in saliva and urine. The levels were significant but still lower than the reference dose for daily ingestion. Copyright © 2016 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.

A comparison of shear bond strength of orthodontic brackets bonded with four different orthodontic adhesives

PubMed Central

Sharma, Sudhir; Tandon, Pradeep; Nagar, Amit; Singh, Gyan P; Singh, Alka; Chugh, Vinay K

2014-01-01

Objectives: The objective of this study is to compare the shear bond strength (SBS) of stainless steel (SS) orthodontic brackets bonded with four different orthodontic adhesives. Materials and Methods: Eighty newly extracted premolars were bonded to 0.022 SS brackets (Ormco, Scafati, Italy) and equally divided into four groups based on adhesive used: (1) Rely-a-Bond (self-cure adhesive, Reliance Orthodontic Product, Inc., Illinois, USA), (2) Transbond XT (light-cure adhesive, 3M Unitek, CA, USA), (3) Transbond Plus (sixth generation self-etch primer, 3M Unitek, CA, USA) with Transbond XT (4) Xeno V (seventh generation self-etch primer, Dentsply, Konstanz, Germany) with Xeno Ortho (light-cure adhesive, Dentsply, Konstanz, Germany) adhesive. Brackets were debonded with a universal testing machine (Model No. 3382 Instron Corp., Canton, Mass, USA). The adhesive remnant index (ARI) was recordedIn addition, the conditioned enamel surfaces were observed under a scanning electron microscope (SEM). Results: Transbond XT (15.49 MPa) attained the highest bond strength. Self-etching adhesives (Xeno V, 13.51 MPa; Transbond Plus, 11.57 MPa) showed clinically acceptable SBS values and almost clean enamel surface after debonding. The analysis of variance (F = 11.85, P < 0.0001) and Chi-square (χ2 = 18.16, P < 0.05) tests revealed significant differences among groups. The ARI score of 3 (i.e., All adhesives left on the tooth) to be the most prevalent in Transbond XT (40%), followed by Rely-a-Bond (30%), Transbond Plus with Transbond XT (15%), and Xeno V with Xeno Ortho (10%). Under SEM, enamel surfaces after debonding of the brackets appeared porous when an acid-etching process was performed on the surfaces of Rely-a-Bond and Transbond XT, whereas with self-etching primers enamel presented smooth and almost clean surfaces (Transbond Plus and Xeno V group). Conclusion: All adhesives yielded SBS values higher than the recommended bond strength (5.9-7–8 MPa), Seventh generation self-etching primer Xeno V with Xeno Ortho showed clinically acceptable SBS and the least amount of residual adhesive left on the enamel surface after debonding. PMID:24987660

Red-Shifting versus Blue-Shifting Hydrogen Bonds: Perspective from Ab Initio Valence Bond Theory.

PubMed

Chang, Xin; Zhang, Yang; Weng, Xinzhen; Su, Peifeng; Wu, Wei; Mo, Yirong

2016-05-05

Both proper, red-shifting and improper, blue-shifting hydrogen bonds have been well-recognized with enormous experimental and computational studies. The current consensus is that there is no difference in nature between these two kinds of hydrogen bonds, where the electrostatic interaction dominates. Since most if not all the computational studies are based on molecular orbital theory, it would be interesting to gain insight into the hydrogen bonds with modern valence bond (VB) theory. In this work, we performed ab initio VBSCF computations on a series of hydrogen-bonding systems, where the sole hydrogen bond donor CF3H interacts with ten hydrogen bond acceptors Y (═NH2CH3, NH3, NH2Cl, OH(-), H2O, CH3OH, (CH3)2O, F(-), HF, or CH3F). This series includes four red-shifting and six blue-shifting hydrogen bonds. Consistent with existing findings in literature, VB-based energy decomposition analyses show that electrostatic interaction plays the dominating role and polarization plays the secondary role in all these hydrogen-bonding systems, and the charge transfer interaction, which denotes the hyperconjugation effect, contributes only slightly to the total interaction energy. As VB theory describes any real chemical bond in terms of pure covalent and ionic structures, our fragment interaction analysis reveals that with the approaching of a hydrogen bond acceptor Y, the covalent state of the F3C-H bond tends to blue-shift, due to the strong repulsion between the hydrogen atom and Y. In contrast, the ionic state F3C(-) H(+) leads to the red-shifting of the C-H vibrational frequency, owing to the attraction between the proton and Y. Thus, the relative weights of the covalent and ionic structures essentially determine the direction of frequency change. Indeed, we find the correlation between the structural weights and vibrational frequency changes.

Comparative evaluation of tensile bond strength and microleakage of conventional glass ionomer cement, resin modified glass ionomer cement and compomer: An in vitro study.

PubMed

Rekha, C Vishnu; Varma, Balagopal; Jayanthi

2012-07-01

The purpose of this study was to evaluate and compare the tensile bond strength and microleakage of Fuji IX GP, Fuji II LC, and compoglass and to compare bond strength with degree of microleakage exhibited by the same materials. Occlusal surfaces of 96 noncarious primary teeth were ground perpendicular to long axis of the tooth. Preparations were distributed into three groups consisting of Fuji IX GP, Fuji II LC and Compoglass. Specimens were tested for tensile bond strength by mounting them on Instron Universal Testing Machine. Ninety-six primary molars were treated with Fuji IX GP, Fuji II LC, and compoglass on box-only prepared proximal surface. Samples were thermocycled, stained with dye, sectioned, and scored for microleakage under stereomicroscope. ANOVA and Bonferrani correction test were done for comparisons. Pearson Chi-square test and regression analysis were done to assess the association between the parameters. Compoglass showed highest tensile strength and Fuji II LC showed least microleakage. There was a significant difference between the three groups in tensile strength and microleakage levels. The correlation between tensile strength and microleakage level in each group showed that there was a significant negative correlation only in Group 3. Fuji II LC and compoglass can be advocated in primary teeth because of their superior physical properties when compared with Fuji IX GP.

Electronegativity effects and single covalent bond lengths of molecules in the gas phase.

PubMed

Lang, Peter F; Smith, Barry C

2014-06-07

This paper discusses in detail the calculation of internuclear distances of heteronuclear single bond covalent molecules in the gaseous state. It reviews briefly the effect of electronegativity in covalent bond length. A set of single bond covalent radii and electronegativity values are proposed. Covalent bond lengths calculated by an adapted form of a simple expression (which calculated internuclear separation of different Group 1 and Group 2 crystalline salts to a remarkable degree of accuracy) show very good agreement with observed values. A small number of bond lengths with double bonds as well as bond lengths in the crystalline state are calculated using the same expression and when compared with observed values also give good agreement. This work shows that covalent radii are not additive and that radii in the crystalline state are different from those in the gaseous state. The results also show that electronegativity is a major influence on covalent bond lengths and the set of electronegativity scale and covalent radii proposed in this work can be used to calculate covalent bond lengths in different environments that have not yet been experimentally measured.

Design/Analysis of Metal/Composite Bonded Joints for Survivability at Cryogenic Temperatures

NASA Technical Reports Server (NTRS)

Bartoszyk, Andrew E.

2004-01-01

A major design and analysis challenge for the JWST ISM structure is the metal/composite bonded joints that will be required to survive down to an operational ultra-low temperature of 30K (-405 F). The initial and current baseline design for the plug-type joint consists of a titanium thin walled fitting (1-3mm thick) bonded to the interior surface of an M555/954-6 composite truss square tube with an axially stiff biased lay-up. Metallic fittings are required at various nodes of the truss structure to accommodate instrument and lift-point bolted interfaces. Analytical experience and design work done on metal/composite bonded joints at temperatures below liquid nitrogen are limited and important analysis tools, material properties, and failure criteria for composites at cryogenic temperatures are virtually nonexistent. Increasing the challenge is the difficulty in testing for these required tools and parameters at 30K. A preliminary finite element analysis shows that failure due to CTE mismatch between the biased composite and titanium or aluminum is likely. Failure is less likely with Invar, however an initial mass estimate of Invar fittings demonstrates that Invar is not an automatic alternative. In order to gain confidence in analyzing and designing the ISM joints, a comprehensive joint development testing program has been planned and is currently running. The test program is designed for the correlation of the analysis methodology, including tuning finite element model parameters, and developing a composite failure criterion for the effect of multi-axial composite stresses on the strength of a bonded joint at 30K. The testing program will also consider stress mitigation using compliant composite layers and potential strength degradation due to multiple thermal cycles. Not only will the finite element analysis be correlated to the test data, but the FEA will be used to guide the design of the test. The first phase of the test program has been completed and the preliminary analysis has been revisited based on the test data In this work, we present an overview of the test plan, results today, and resulting design improvements.

Extension of the carotenoid test to superficially porous C18 bonded phases, aromatic ligand types and new classical C18 bonded phases.

PubMed

Lesellier, E

2012-11-30

The recent introduction of new stationary phases for liquid chromatography based on superficially porous particles, called core-shell or fused-core, dramatically improved the separation performances through very high efficiency, due mainly to reduced eddy diffusion. However, few studies have evaluated the retention and selectivity of C18 phases based on such particles, despite some retention order change reported in literature between some of these phases. The carotenoid test has been developed a few years ago in the goal to compare the chromatographic properties of C18 bonded phases. Based on the analysis of carotenoid pigments by using Supercritical Fluid Chromatography (SFC), it allows, with a single analysis, to measure three main properties of reversed phase chromatography stationary phases: hydrophobicity, polar surface activity and shape selectivity. Previous studies showed the effect of the endcapping treatment, the bonding density, the pore size, and the type of bonding (monomeric vs. polymeric) on these studied properties, and described the classification map used for a direct column comparison. It was applied to ten ODS superficially porous stationary phases, showing varied chromatographic behaviors amongst these phases. As expected, due to the lower specific surface area, these superficially porous phases are less hydrophobic than the fully porous one. In regards of the polar surface activity (residual silanols) and to the shape selectivity, some of these superficially porous phases display close chromatographic properties (Poroshell 120, Halo C18, Ascentis Express, Accucore C18, Nucleoshell C18 on one side and Aeris Wide pore, Aeris peptide and Kinetex XDB on the other side), whereas others, Kinetex C18 and Halo peptide ES C18 display more specific ones. Besides, they can be compared to classical fully porous phases, in the goal to improve method transfer from fully to superficially porous particles. By the way, the paper also report the extension of the test to other ligands such as naphtyl, cholester, phenyl-hexyl, or to the new ODS bonded phases, such as charge surface hybrid phases, High Strength Silica, and Hybrid ones, and also presents results for identical brands using different particle size, such as Luna and Synergi phases. Phenyl-hexyl and napthyl ligands show rather close properties, low hydrophobicity, high polar surface activity and specific shape selectivity, whereas, at the opposite, the cholester phase display a polymeric behavior and a high hydrophobicity. Finally, additional classical (fully porous particles) C18 bonded phases are also reported to complete the data set presented in previous papers. Copyright © 2012 Elsevier B.V. All rights reserved.

A combined variable temperature 600 MHz NMR/MD study of the calcium release agent cyclic adenosine diphosphate ribose (cADPR): Structure, conformational analysis, and thermodynamics of the conformational equilibria.

PubMed

Javornik, Uroš; Plavec, Janez; Wang, Baifan; Graham, Steven M

2018-01-02

A combined variable temperature 600 MHz NMR/molecular dynamics study of the Ca 2+ -release agent cyclic adenosine 5'-diphosphate ribose (cADPR) was conducted. In addition to elucidating the major and minor orientations of the conformationally flexible furanose rings, γ- (C4'-C5'), and β- (C5'-O5') bonds, the thermodynamics (ΔH o , ΔS o ) associated with each of these conformational equilibria were determined. Both furanose rings were biased towards a south conformation (64-74%) and both β-bonds heavily favored trans conformations. The R-ring γ-bond was found to exist almost exclusively as the γ + conformer, whereas the A-ring γ-bond was a mixture of the γ + and γ t conformers, with the trans conformer being slightly favored. Enthalpic factors accounted for most of the observed conformational preferences, although the R-ring furanose exists as its major conformation based solely on entropic factors. There was excellent agreement between the NMR and MD results, particularly with regard to the conformer identities, but the MD showed a bias towards γ + conformers. The MD results showed that both N-glycosidic χ-bonds are exclusively syn. Collectively the data allowed for the construction of a model for cADPR in which many of the conformationally flexible units in fact effectively adopt single orientations and where most of the conformational diversity resides in its A-ring furanose and γ-bond. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microbial complexes levels in conventional and self-ligating brackets.

PubMed

Bergamo, Ana Zilda Nazar; Nelson-Filho, Paulo; Andrucioli, Marcela Cristina Damião; do Nascimento, Cássio; Pedrazzi, Vinícius; Matsumoto, Mírian Aiko Nakane

2017-05-01

The aims were to evaluate the levels of bacterial species in saliva and in situ and to assess whether the design of brackets influences the risk of developing periodontal disease. Twenty patients (13.3 mean age) were bonded with self-ligating brackets and a conventional bracket. Saliva was collected before bonding and 30 and 60 days after bonding. One sample of each bracket was removed 30 and 60 days after bonding. The analysis was determined by checkerboard DNA-DNA hybridization. The data was evaluated by the non-parametric test. A significant increase in the levels of bacterial species in the saliva occurred in 15 of the 22 analyzed species. The self-ligating brackets presented the highest incidence percentages for the orange and red complexes 60 days after bonding. In situ analyses showed different patterns according to the bracket design. The levels of Campylobacter rectus showed significant differences (p = 0.011) 60 days after bonding among the three brackets; the highest values were observed in the In-Ovation®R bracket. The bracket design seems to influence the levels of bacterial species involved in periodontal disease. Considering the wide variety of bacterial species, additional studies are needed to aid in the establishment of effective protocols to prevent the development of periodontal disease during orthodontic treatment. A dynamic alteration in the oral microbiota may lead to inflammatory reactions in the supporting soft and hard tissues. The different types of brackets interfere with bacterial adherence. Bracket design should be considered in orthodontic treatment.

27 CFR 19.167 - Increase of bond coverage.

Code of Federal Regulations, 2014 CFR

2014-04-01

... separate strengthening bond in accordance with paragraph (b) of this section. (b) Strengthening bonds. A strengthening bond is a second bond with the same surety as on the original bond which covers the increased liability. A strengthening bond must show both its execution date and its effective date. TTB will not...

27 CFR 19.167 - Increase of bond coverage.

Code of Federal Regulations, 2013 CFR

2013-04-01

... separate strengthening bond in accordance with paragraph (b) of this section. (b) Strengthening bonds. A strengthening bond is a second bond with the same surety as on the original bond which covers the increased liability. A strengthening bond must show both its execution date and its effective date. TTB will not...

27 CFR 19.167 - Increase of bond coverage.

Code of Federal Regulations, 2012 CFR

2012-04-01

... separate strengthening bond in accordance with paragraph (b) of this section. (b) Strengthening bonds. A strengthening bond is a second bond with the same surety as on the original bond which covers the increased liability. A strengthening bond must show both its execution date and its effective date. TTB will not...

27 CFR 19.167 - Increase of bond coverage.

Code of Federal Regulations, 2011 CFR

2011-04-01

... separate strengthening bond in accordance with paragraph (b) of this section. (b) Strengthening bonds. A strengthening bond is a second bond with the same surety as on the original bond which covers the increased liability. A strengthening bond must show both its execution date and its effective date. TTB will not...

Stacking interactions of hydrogen-bridged rings – stronger than the stacking of benzene molecules.

PubMed

Blagojević, Jelena P; Zarić, Snežana D

2015-08-21

Analysis of crystal structures from the Cambridge Structural Database showed that 27% of all planar five-membered hydrogen-bridged rings, possessing only single bonds within the ring, form intermolecular stacking interactions. Interaction energy calculations show that interactions can be as strong as -4.9 kcal mol(-1), but dependent on ring structure.

Thermodynamics, Kinetics and Structural Evolution of ε-LiVOPO 4 over Multiple Lithium Intercalation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yuh-Chieh; Wen, Bohua; Wiaderek, Kamila M.

In this work, we demonstrate the stable cycling of more than one Li in solid-state-synthesized ε-LiVOPO4 over more than 20 cycles for the first time. Using a combination of density functional theory (DFT) calculations, X-ray pair distribution function (PDF) analysis and X-ray absorption near edge structure (XANES) measurements, we present a comprehensive analysis of the thermodynamics, kinetics, and structural evolution of ε-LixVOPO4 over the entire lithiation range. We identify two intermediate phases at x = 1.5 and 1.75 in the low-voltage regime using DFT calculations, and the computed and electrochemical voltage profiles are in excellent agreement. Operando PDF and EXAFSmore » techniques show a reversible hysteretic change in the short (<2 Å) V—O bond lengths coupled with an irreversible extension of the long V—O bond (>2.4 Å) during low-voltage cycling. Hydrogen intercalation from electrolyte decomposition is a possible explanation for the ~2.4 Å V—O bond and its irreversible extension. Finally, we show that ε-LixVOPO4 is likely a pseudo-1D ionic diffuser with low electronic conductivity using DFT calculations, which suggests that nanosizing and carbon coating is necessary to achieve good electrochemical performance in this material.« less

Carbon Dioxide Absorption by the Imidazolium-Amino Acid Ionic Liquids, Kinetics, and Mechanism Approach.

PubMed

Rezaeian, Mojtaba; Izadyar, Mohammad; Nakhaei Pour, Ali

2018-06-25

The kinetics and mechanism of CO 2 absorption by ionic liquids (ILs) were studied, theoretically. The studied ILs are composed of 1-ethyl-3-methylimidazolium [Emim] + as the cation with a general formula of the [Emim][X] (X = Gly - , Ala - , Lys - , Arg - ). To investigate the alkyl chain length and the number of the amine group effects on the CO 2 absorption, different amino acid anions were chosen. On the basis of the enthalpy changes during CO 2 capture, a chemisorption nature is confirmed. An increase in the number of amine (-NH 2 ) groups in the ILs structures, facilitates the CO 2 absorption. According to kinetic results, the rate of CO 2 absorption by [Emim][Gly] is higher than that of [Emim][Ala]. This can be interpreted by a higher steric hindrance in [Emim][Ala] due to an additional methyl group in the amino acid chain. Donor-acceptor interactions and C-N bond formation were investigated by natural bond orbital analysis. Moreover, topological studies show a covalent nature for the C-N bond critical point that showing CO 2 capture is a chemisorption process. Finally, on the basis of kinetic energy results, donor-acceptor interaction and topological analysis, [Emim][Arg] is proposed as the best candidate for CO 2 absorption from the kinetic and thermodynamic viewpoints.

Energy decomposition analysis of single bonds within Kohn-Sham density functional theory.

PubMed

Levine, Daniel S; Head-Gordon, Martin

2017-11-28

An energy decomposition analysis (EDA) for single chemical bonds is presented within the framework of Kohn-Sham density functional theory based on spin projection equations that are exact within wave function theory. Chemical bond energies can then be understood in terms of stabilization caused by spin-coupling augmented by dispersion, polarization, and charge transfer in competition with destabilizing Pauli repulsions. The EDA reveals distinguishing features of chemical bonds ranging across nonpolar, polar, ionic, and charge-shift bonds. The effect of electron correlation is assessed by comparison with Hartree-Fock results. Substituent effects are illustrated by comparing the C-C bond in ethane against that in bis(diamantane), and dispersion stabilization in the latter is quantified. Finally, three metal-metal bonds in experimentally characterized compounds are examined: a [Formula: see text]-[Formula: see text] dimer, the [Formula: see text]-[Formula: see text] bond in dizincocene, and the Mn-Mn bond in dimanganese decacarbonyl.

19 CFR Appendix C to Part 113 - Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows

Code of Federal Regulations, 2011 CFR

2011-04-01

... 19 Customs Duties 1 2011-04-01 2011-04-01 false Bond for Deferral of Duty on Large Yachts Imported... Appendix C to Part 113—Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows ____, as...

19 CFR Appendix C to Part 113 - Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows

Code of Federal Regulations, 2010 CFR

2010-04-01

... 19 Customs Duties 1 2010-04-01 2010-04-01 false Bond for Deferral of Duty on Large Yachts Imported... Appendix C to Part 113—Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows ____, as...

Visualizing Chemical Bonds in Synthetic Molecules

NASA Astrophysics Data System (ADS)

Collins, Laura C.; Ruth, Anthony; Green, David B.; Janko, Boldizsar; Gomes, Kenjiro K.

The use of synthetic quantum systems makes it possible to study phenomena that cannot be probed by conventional experiments. We created synthetic molecules using atomic manipulation and directly imaged the chemical bonds using tunneling spectroscopy. These synthetic systems allow us to probe the structure and electronic properties of chemical bonds in molecules, including those that would be unstable in nature, with unprecedented detail. The experimental images of electronic states in our synthetic molecules show a remarkable match to the charge distribution predicted by density functional theory calculations. The statistical analysis of the spectroscopy of these molecules can be adapted in the future to quantify aromaticity, which has been difficult to quantify universally thus far due to vague definitions. We can also study anti-aromatic molecules which are unstable naturally, to illuminate the electronic consequences of antiaromaticity.

Stability, elastic and electronic properties of a novel BN2 sheet with extended hexagons with N-N bonds

NASA Astrophysics Data System (ADS)

Waters, Kevin; Pandey, Ravindra

2018-04-01

A new B-N monolayer material (BN2) consisting of a network of extended hexagons is predicted using density functional theory. The distinguishable nature of this 2D material is found to be the presence of the bonded N atoms (N-N) in the lattice. Analysis of the phonon dispersion curves show this phase of BN2 to be stable. The calculated elastic properties exhibit anisotropic mechanical properties that surpass graphene in the armchair direction. The BN2 monolayer is metallic with in-plane p states dominating the Fermi level. Novel applications resulting from a strong anisotropic mechanical strength together with the metallic properties of the BN2 sheet with the extended hexagons with N-N bonds may enable future innovation at the nanoscale.

Near-neighbor mixing and bond dilation in mechanically alloyed Cu-Fe

NASA Astrophysics Data System (ADS)

Harris, V. G.; Kemner, K. M.; Das, B. N.; Koon, N. C.; Ehrlich, A. E.; Kirkland, J. P.; Woicik, J. C.; Crespo, P.; Hernando, A.; Garcia Escorial, A.

1996-09-01

Extended x-ray-absorption fine-structure (EXAFS) measurements were used to obtain element-specific, structural, and chemical information of the local environments around Cu and Fe atoms in high-energy ball-milled CuxFe1-x samples (x=0.50 and 0.70). Analysis of the EXAFS data shows both Fe and Cu atoms reside in face-centered-cubic sites where the first coordination sphere consists of a mixture of Fe and Cu atoms in a ratio which reflects the as-prepared stoichiometry. The measured bond distances indicate a dilation in the bonds between unlike neighbors which accounts for the lattice expansion measured by x-ray diffraction. These results indicate that metastable alloys having a positive heat of mixing can be prepared via the high-energy ball-milling process.

Study of the cross-market effects of Brexit based on the improved symbolic transfer entropy GARCH model—An empirical analysis of stock–bond correlations

PubMed Central

Chen, Xiurong; Zhao, Rubo

2017-01-01

In this paper, we study the cross-market effects of Brexit on the stock and bond markets of nine major countries in the world. By incorporating information theory, we introduce the time-varying impact weights based on symbolic transfer entropy to improve the traditional GARCH model. The empirical results show that under the influence of Brexit, flight-to-quality not only commonly occurs between the stocks and bonds of each country but also simultaneously occurs among different countries. We also find that the accuracy of the time-varying symbolic transfer entropy GARCH model proposed in this paper has been improved compared to the traditional GARCH model, which indicates that it has a certain practical application value. PMID:28817712

Effect of different surface treatments on shear bond strength of zirconia to three resin cements

NASA Astrophysics Data System (ADS)

Dadjoo, Nisa

Statement of problem: There are no standard guidelines for material selection to obtain acceptable bonding to high-strength zirconium oxide ceramic. Studies suggest resin cements in combination with MDP-containing primer is a reasonable choice, however, the other cements cannot be rejected and need further investigation. Objective: The purpose of this in vitro study was the evaluation of the shear bond strength of three composite resin cements to zirconia ceramic after using different surface conditioning methods. Materials and methods: One hundred and twenty sintered Y-TZP ceramic (IPS e.max ZirCAD) squares (8 x 8 x 4 mm) were embedded in acrylic molds, then divided into three groups (n=40) based on the type of cement used. Within each group, the specimens were divided into four subgroups (n=10) and treated as follows: (1) Air abrasion with 50microm aluminum oxide (Al2O 3) particles (ALO); (2) Air abrasion + Scotchbond Universal adhesive (SBU); (3) Air abrasion + Monobond Plus (MBP); (4) Air abrasion + Z-Prime Plus (ZPP). Composite cylinders were used as carriers to bond to conditioned ceramic using (1) RelyX Ultimate adhesive resin cement (RX); (2) Panavia SA self-adhesive resin cement (PSA); (3) Calibra esthetic cement (CAL). The bonded specimens were submerged in distilled water and subjected to 24-hour incubation period at 37°C. All specimens were stressed in shear at a constant crosshead speed of 0.5 mm/min until failure. Statistical analysis was performed by ANOVA. The bond strength values (MPa), means and standard deviations were calculated and data were analyzed using analysis of variance with Fisher's PLSD multiple comparison test at the 0.05 level of significance. The nature of failure was recorded. Results: The two-way ANOVA showed Panavia SA to have the highest strength at 44.3 +/- 16.9 MPa (p<0.05). The combination of Scotchbond Universal surface treatment with Panavia SA cement showed statistically higher bond strength (p=0.0054). The highest bond strengths for all three cements were observed with Scotchbond Universal surface treatment (p=0.0041). Calibra in combination with aluminum oxide air abrasion resulted in statistically lowest bond strength at 12.0 +/- 3.9 MPa. The predominant mode of failure was cohesive with cement remaining principally on the zirconium oxide samples in 57.5% of the specimens, followed by cement found on both the zirconium oxide samples and composite rods (mixed) in 32.5% of the samples. Only 10% of the specimens were found with cement on the composite rods (adhesive failure). Conclusions: Within the limitations of this in vitro study, the MDP-containing resin cement, Panavia SA, yielded the strongest bond to Y-TZP ceramic when compared to adhesive (RelyX Ultimate) or esthetic (Calibra) resin cements. Air abrasion particle + Scotchbond Universal surface treatment demonstrated the highest bond strength regardless of the cement. Significance: The variation of surface conditioning methods yielded different results in accordance with the cement types. Overall, Scotchbond Universal adhesive + air abrasion yielded the highest bond strengths among all three surface treatments. The phosphate monomer-containing luting system, Panavia SA, is acceptable for bonding to zirconia ceramics.

An extracellular disulfide bond forming protein (DsbF) from Mycobacterium tuberculosis: Structural, biochemical and gene expression analysis

PubMed Central

Chim, Nicholas; Riley, Robert; The, Juliana; Im, Soyeon; Segelke, Brent; Lekin, Tim; Yu, Minmin; Hung, Li Wei; Terwilliger, Tom; Whitelegge, Julian P.; Goulding, Celia W.

2010-01-01

Disulfide bond forming (Dsb) proteins ensure correct folding and disulfide bond formation of secreted proteins. Previously, we showed that Mycobacterium tuberculosis DsbE (Mtb DsbE, Rv2878c) aids in vitro oxidative folding of proteins. Here we present structural, biochemical and gene expression analyses of another putative Mtb secreted disulfide bond isomerase protein homologous to Mtb DsbE, Mtb DsbF (Rv1677). The X-ray crystal structure of Mtb DsbF reveals a conserved thioredoxin fold although the active-site cysteines may be modeled in both oxidized and reduced forms, in contrast to the solely reduced form in Mtb DsbE. Furthermore, the shorter loop region in Mtb DsbF results in a more solvent-exposed active site. Biochemical analyses show that, similar to Mtb DsbE, Mtb DsbF can oxidatively refold reduced, unfolded hirudin and has a comparable pKa for the active-site solvent-exposed cysteine. However, contrary to Mtb DsbE, the Mtb DsbF redox potential is more oxidizing and its reduced state is more stable. From computational genomics analysis of the M. tuberculosis genome, we identified a potential Mtb DsbF interaction partner, Rv1676, a predicted peroxiredoxin. Complex formation is supported by protein co-expression studies and inferred by gene expression profiles, whereby Mtb DsbF and Rv1676 are upregulated under similar environments. Additionally, comparison of Mtb DsbF and Mtb DsbE gene expression data indicate anticorrelated gene expression patterns, suggesting that these two proteins and their functionally linked partners constitute analogous pathways that may function under different conditions. PMID:20060836

Self-initiation of UV photopolymerization reactions using tetrahalogenated bisphenol A (meth)acrylates.

PubMed

Pelras, Théophile; Knolle, Wolfgang; Naumov, Sergej; Heymann, Katja; Daikos, Olesya; Scherzer, Tom

2017-05-17

The potential of tetrachlorinated and tetrabrominated bisphenol A diacrylates and dimethacrylates for self-initiation of a radical photopolymerization was investigated. The kinetics of the photopolymerization of an acrylic model varnish containing halogenated monomers was studied by real-time FTIR spectroscopy, whereas the formation of reactive species and secondary products was elucidated by laser flash photolysis and product analysis by GC-MS after steady-state photolysis. The interpretation of the experimental data and the analysis of possible reaction pathways were assisted by quantum chemical calculations. It was shown that all halogenated monomers lead to a significant acceleration of the photopolymerization kinetics at a minimum concentration of 5 wt%. Steady-state and laser flash photolysis measurements as well as quantum chemical calculations showed that brominated and chlorinated samples do not follow the same pathway to generate radical species. Whereas chlorinated (meth)acrylates may cleave only at the C-O bonds of the carboxyl groups resulting in acrolein and oxyl radicals for initiation, brominated monomers may cleave either at the C-O bonds or at the C-Br bonds delivering aryl and bromine radicals. The quantum yields for the photolysis of the halogenated monomers were found to be in the order of 0.1 for acrylates and 0.2 for methacrylates (with an estimated error of 25%), independently of the attached Br and Cl halogens. Finally, the trihalogenated bisphenol A di(meth)acrylate radicals and the acrolein radicals were found to show the highest efficiencies for the reaction with another acrylic double bond leading to the formation of a polymer network.

Effect of various bleaching treatments on shear bond strength of different universal adhesives and application modes

PubMed Central

2018-01-01

Objectives The aim of this in vitro study was to evaluate the bond strength of 2 universal adhesives used in different application modes to bleached enamel. Materials and Methods Extracted 160 sound human incisors were used for the study. Teeth were divided into 4 treatment groups: No treatment, 35% hydrogen peroxide, 16% carbamid peroxide, 7.5% carbamid peroxide. After bleaching treatments, groups were divided into subgroups according to the adhesive systems used and application modes (n = 10): 1) Single Bond Universal, etch and rinse mode; 2) Single Bond Universal, self-etch mode; 3) Gluma Universal, etch and rinse mode; 4) Gluma Universal, self-etch mode. After adhesive procedures nanohybrid composite resin cylinders were bonded to the enamel surfaces. All specimens were subjected to shear bond strength (SBS) test after thermocycling. Data were analyzed using a 3-way analysis of variance (ANOVA) and Tukey post hoc test. Results No significant difference were found among bleaching groups (35% hydrogen peroxide, 16% carbamid peroxide, 7.5% carbamid peroxide, and no treatment groups) in the mean SBS values. There was also no difference in SBS values between Single Bond Universal and Gluma Universal at same application modes, whereas self-etch mode showed significantly lower SBS values than etch and rinse mode (p < 0.05). Conclusions The bonding performance of the universal adhesives was enhanced with the etch and rinse mode application to bleached enamel and non-bleached enamel. PMID:29765900

Human acid sphingomyelinase.

PubMed

Lansmann, Stephanie; Schuette, Christina G; Bartelsen, Oliver; Hoernschemeyer, Joerg; Linke, Thomas; Weisgerber, Judith; Sandhoff, Konrad

2003-03-01

Human acid sphingomyelinase (haSMase, EC 3.1.4.12) catalyzes the lysosomal degradation of sphingomyelin to ceramide and phosphorylcholine. An inherited haSMase deficiency leads to Niemann-Pick disease, a severe sphingolipid storage disorder. The enzyme was purified and cloned over 10 years ago. Since then, only a few structural properties of haSMase have been elucidated. For understanding of its complex functions including its role in certain signaling and apoptosis events, complete structural information about the enzyme is necessary. Here, the identification of the disulfide bond pattern of haSMase is reported for the first time. Functional recombinant enzyme expressed in SF21 cells using the baculovirus expression system was purified and digested by trypsin. MALDI-MS analysis of the resulting peptides revealed the four disulfide bonds Cys120-Cys131, Cys385-Cys431, Cys584-Cys588 and Cys594-Cys607. Two additional disulfide bonds (Cys221-Cys226 and Cys227-Cys250) which were not directly accessible by tryptic cleavage, were identified by a combination of a method of partial reduction and MALDI-PSD analysis. In the sphingolipid activator protein (SAP)-homologous N-terminal domain of haSMase, one disulfide bond was assigned as Cys120-Cys131. The existence of two additional disulfide bridges in this region was proved, as was expected for the known disulfide bond pattern of SAP-type domains. These results support the hypothesis that haSMase possesses an intramolecular SAP-type activator domain as predicted by sequence comparison [Ponting, C.P. (1994) Protein Sci., 3, 359-361]. An additional analysis of haSMase isolated from human placenta shows that the recombinant and the native human protein possess an identical disulfide structure.

System analysis through bond graph modeling

NASA Astrophysics Data System (ADS)

McBride, Robert Thomas

2005-07-01

Modeling and simulation form an integral role in the engineering design process. An accurate mathematical description of a system provides the design engineer the flexibility to perform trade studies quickly and accurately to expedite the design process. Most often, the mathematical model of the system contains components of different engineering disciplines. A modeling methodology that can handle these types of systems might be used in an indirect fashion to extract added information from the model. This research examines the ability of a modeling methodology to provide added insight into system analysis and design. The modeling methodology used is bond graph modeling. An investigation into the creation of a bond graph model using the Lagrangian of the system is provided. Upon creation of the bond graph, system analysis is performed. To aid in the system analysis, an object-oriented approach to bond graph modeling is introduced. A framework is provided to simulate the bond graph directly. Through object-oriented simulation of a bond graph, the information contained within the bond graph can be exploited to create a measurement of system efficiency. A definition of system efficiency is given. This measurement of efficiency is used in the design of different controllers of varying architectures. Optimal control of a missile autopilot is discussed within the framework of the calculated system efficiency.

Acousto-optic signature analysis for inspection of the orbiter thermal protection tile bonds

NASA Technical Reports Server (NTRS)

Rodriguez, Julio G.; Tow, D. M.; Barna, B. A.

1990-01-01

The goal of this research is to develop a viable NDE technique for the inspection of orbiter thermal protection system (TPS) tile bonds. Phase 2, discussed here, concentrated on developing an empirical understanding of the bonded and unbonded vibration signatures of acreage tiles. Controlled experiments in the laboratory have provided useful information on the dynamic response of TPS tiles. It has been shown that several signatures are common to all the pedigree tiles. This degree of consistency in the tile-SIP (strain isolation pad) dynamic response proves that an unbond can be detected for a known tile and establish the basis for extending the analysis capability to arbitrary tiles for which there are no historical data. The field tests of the noncontacting laser acoustic sensor system, conducted at the Kennedy Space Center (KSC), investigated the vibrational environment of the Orbiter Processing Facility (OPF) and its effect on the measurement and analysis techniques being developed. The data collected showed that for orbiter locations, such as the body flap and elevon, the data analysis scheme, and/or the sensor, will require modification to accommodate the ambient motion. Several methods were identified for accomplishing this, and a solution is seen as readily achievable. It was established that the tile response was similar to that observed in the laboratory. Of most importance, however, is that the field environment will not affect the physics of the dynamic response that is related to bond condition. All of this information is fundamental to any future design and development of a prototype system.

A quality quantitative method of silicon direct bonding based on wavelet image analysis

NASA Astrophysics Data System (ADS)

Tan, Xiao; Tao, Zhi; Li, Haiwang; Xu, Tiantong; Yu, Mingxing

2018-04-01

The rapid development of MEMS (micro-electro-mechanical systems) has received significant attention from researchers in various fields and subjects. In particular, the MEMS fabrication process is elaborate and, as such, has been the focus of extensive research inquiries. However, in MEMS fabrication, component bonding is difficult to achieve and requires a complex approach. Thus, improvements in bonding quality are relatively important objectives. A higher quality bond can only be achieved with improved measurement and testing capabilities. In particular, the traditional testing methods mainly include infrared testing, tensile testing, and strength testing, despite the fact that using these methods to measure bond quality often results in low efficiency or destructive analysis. Therefore, this paper focuses on the development of a precise, nondestructive visual testing method based on wavelet image analysis that is shown to be highly effective in practice. The process of wavelet image analysis includes wavelet image denoising, wavelet image enhancement, and contrast enhancement, and as an end result, can display an image with low background noise. In addition, because the wavelet analysis software was developed with MATLAB, it can reveal the bonding boundaries and bonding rates to precisely indicate the bond quality at all locations on the wafer. This work also presents a set of orthogonal experiments that consist of three prebonding factors, the prebonding temperature, the positive pressure value and the prebonding time, which are used to analyze the prebonding quality. This method was used to quantify the quality of silicon-to-silicon wafer bonding, yielding standard treatment quantities that could be practical for large-scale use.

An experimental and theoretical study of a hydrogen-bonded complex: O-phenylenediamine with 2,6-pyridinedicarboxylic acid

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Habibi-Khorassani, Sayyed Mostafa; Shahraki, Mehdi; Shokrollahi, Ardeshir; Moghimi, Abolghasem; Tamandani, Halimeh Kord; Gavahi, Sara

2015-11-01

The hydrogen-bonded complex, [(OPDH)+(dipicH)-.H2O], between o-phenylenediamine (OPD) and 2,6-pyridinedicarboxylic acid (dipicH2) has been characterized in water by the 1H, 13C NMR and IR spectroscopies. The crystal structure showed that the edge to face C-H⋯π and C-O⋯π stacking interactions between the dipicH2 and OPD rings play an extra significant role in the formation of the hydrogen-bonded complex and supported the H-bonding interactions. The proton transfer also investigated theoretically in gas phase and thermodynamic parameters such as ΔH‡, ΔG‡, ΔS‡ were calculated for this process. Moreover, intramolecular hydrogen-bonding interaction has been recognized by calculating the electron density ρ(r) and Laplacian ∇2ρ(r) at the bond critical point (BCP) using Atoms-In-Molecule (AIM) method and also the interaction between electron acceptor (σ*) of OH with the lone pair of the nitrogen atom as an electron donor using Natural Bond Orbital (NBO) analysis. In addition, the protonation constants of dipicH2 and OPD and the equilibrium constants for the dipic-OPD (1:1) proton transfer system were obtained by the potentiometric pH titration method using the Hyperquad 2008 program. The stoichiometry of the proton transfer species in the solution confirmed the solid state result.

The effect of double-coating and times on the immediate and 6-month dentin bonding of universal adhesives.

PubMed

Pashaev, Diial; Demirci, Mustafa; Tekçe, Neslihan; Tuncer, Safa; Baydemir, Canan

2017-01-01

The purpose of this study was to evaluate the effect of double-application coats and times on microtensile bond strength (μTBS) and adhesive-dentin interfaces created by dentin adhesive systems after 6 months of storage in water. Two-hundred sixteen extracted non-carious human third molars were selected for the study. Single-Bond Universal (SU) and All-Bond Universal (AU), Adper Easy One (Eo) Self-Etch adhesive and Adper Single-Bond 2 (Sb) etch-and-rinse adhesive were applied to a flat dentin surface using three methods (1): dentin adhesives were applied as recommended by the manufacturers; (2): two consecutive coats of dentin adhesives were applied before photo-polymerization; and (3): a single coat of adhesive was applied but with twice the manufacturers recommended application time. Microtensile bond strength was determined either immediately or after 6 months of water storage. Data were analyzed using one-way analysis of variance and Tukey's post-hoc tests. At 24 h, groups 1, 2, and 3 exhibited statistically similar results for all dentin adhesive systems. For AU-Er, group 3 showed significantly higher bond strength than all group of AU-Se after 6 months. Universal adhesives seemed more stable against water degradation than traditional two-step etch-and-rinse and all-in-one systems within the 6-month period.

Microfabrication of plastic-PDMS microfluidic devices using polyimide release layer and selective adhesive bonding

DOE PAGES

Wang, Shuyu; Yu, Shifeng; Lu, Ming; ...

2017-03-15

In this study, we present an improved method to bond poly(dimethylsiloxane) (PDMS) with polyimide (PI) to develop flexible substrate microfluidic devices. The PI film was separately fabricated on a silicon wafer by spin coating followed by thermal treatment to avoid surface unevenness of the flexible substrate. In this way, we could also integrate flexible substrate into standard micro-electromechanical systems (MEMS) fabrication. Meanwhile, the adhesive epoxy was selectively transferred to the PDMS microfluidic device by a stamp-and-stick method to avoid epoxy clogging the microfluidic channels. To spread out the epoxy evenly on the transferring substrate, we used superhydrophilic vanadium oxide filmmore » coated glass as the transferring substrate. After the bonding process, the flexible substrate could easily be peeled off from the rigid substrate. Contact angle measurement was used to characterize the hydrophicity of the vanadium oxide film. X-ray photoelectron spectroscopy analysis was conducted to study the surface of the epoxy. We further evaluated the bonding quality by peeling tests, which showed a maximum bonding strength of 100 kPa. By injecting with black ink, the plastic microfluidic device was confirmed to be well bonded with no leakage for a day under 1 atm. Finally, this proposed versatile method could bond the microfluidic device and plastic substrate together and be applied in the fabrication of some biosensors and lab-on-a-chip systems.« less

Effect of maleic anhydride pretreatment on tensile bond strength of a silicone soft liner to a denture base polymer.

PubMed

Demir, Hakan; Soygun, Koray; Dogan, Arife; Keskin, Selda; Dogan, Orhan Murat; Bolayir, Giray

2011-10-01

To determine the effect of resin surface treatment with dissolved maleic anhydride in butanone added into primer on the tensile bond strength between an acrylic denture base resin and a silicone soft liner. To test tensile bond strength, standard dumbbell-shaped acrylic specimens were prepared. Five experimental groups, including the control, were tested (n = 5). Maleic anhydride solutions prepared in butanone at concentrations of 1%, 5%, 10% or 20% were then mixed with 1 ml of Primo adhesive and the mixtures were applied onto the resin bonding surfaces. Silicone liner material was applied to resin surfaces in the conventional manner. Tensile bond strength of the specimens was measured in a universal testing machine. Fractured surfaces were observed under the scanning electron microscope, and resulting chemical changes with the solutions used were analyzed spectroscopically. The highest bond strength value was obtained for the group treated with 5% maleic anhydride (2.53 ± 0.48 MPa); the lowest value was for the group treated with 20% maleic anhydride (1.59 ± 0.29 MPa). Mixed failure was the dominant type seen in the experimental groups. Spectroscopic analysis showed the interaction of the anhydride carbonyl groups with the Primo primer. The treatment of resin surfaces with maleic anhydride added to Primo adhesive effectively increased bond strength between silicone soft liner and denture base resin.

Microfabrication of plastic-PDMS microfluidic devices using polyimide release layer and selective adhesive bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Shuyu; Yu, Shifeng; Lu, Ming

In this study, we present an improved method to bond poly(dimethylsiloxane) (PDMS) with polyimide (PI) to develop flexible substrate microfluidic devices. The PI film was separately fabricated on a silicon wafer by spin coating followed by thermal treatment to avoid surface unevenness of the flexible substrate. In this way, we could also integrate flexible substrate into standard micro-electromechanical systems (MEMS) fabrication. Meanwhile, the adhesive epoxy was selectively transferred to the PDMS microfluidic device by a stamp-and-stick method to avoid epoxy clogging the microfluidic channels. To spread out the epoxy evenly on the transferring substrate, we used superhydrophilic vanadium oxide filmmore » coated glass as the transferring substrate. After the bonding process, the flexible substrate could easily be peeled off from the rigid substrate. Contact angle measurement was used to characterize the hydrophicity of the vanadium oxide film. X-ray photoelectron spectroscopy analysis was conducted to study the surface of the epoxy. We further evaluated the bonding quality by peeling tests, which showed a maximum bonding strength of 100 kPa. By injecting with black ink, the plastic microfluidic device was confirmed to be well bonded with no leakage for a day under 1 atm. Finally, this proposed versatile method could bond the microfluidic device and plastic substrate together and be applied in the fabrication of some biosensors and lab-on-a-chip systems.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Waltmann, Curt; Horst, Nathan; Travesset, Alex

In this work, we present a detailed analysis of the interaction between two nanocrystals capped with ligands consisting of hydrocarbon chains by united atom molecular dynamics simulations. We show that the bonding of two nanocrystals is characterized by ligand textures in the form of vortices. These results are generalized to nanocrystals of different types (differing core and ligand sizes) where the structure of the vortices depends on the softness asymmetry. We provide rigorous calculations for the binding free energy, show that these energies are independent of the chemical composition of the cores, and derive analytical formulas for the equilibrium separation.more » We discuss the implications of our results for the self-assembly of single-component and binary nanoparticle superlattices. Overall, our results show that the structure of the ligands completely determines the bonding of nanocrystals, fully supporting the predictions of the recently proposed Orbifold topological model.« less

A pseudoatom in a cage: trimetallofullerene Y(3)@C(80) mimics y(3)n@c(80) with nitrogen substituted by a pseudoatom.

PubMed

Popov, Alexey A; Zhang, Lin; Dunsch, Lothar

2010-02-23

Y(3)C(80) obtained in the synthesis of nitride clusterfullerenes Y(3)N@C(2n) (2n = 80-88) by the reactive atmosphere method is found to be a genuine trimetallofullerene, Y(3)@C(80), with low ionization potential and divalent state of yttrium atoms. DFT studies of the electronic structure of Y(3)@C(80) show that this molecule mimics Y(3)N@C(80) with the pseudoatom (PA) instead of the nitrogen atom. Topology analysis of the electron density and electron localization function show that yttrium atoms form Y-PA bonds rather than direct Y-Y bonds. Molecular dynamics simulations show that the Y(3)PA cluster is as rigid as Y(3)N and rotates inside the fullerene cage as a single entity.

Design/Analysis of the JWST ISIM Bonded Joints for Survivability at Cryogenic Temperatures

NASA Technical Reports Server (NTRS)

Bartoszyk, Andrew; Johnston, John; Kaprielian, Charles; Kuhn, Jonathan; Kunt, Cengiz; Rodini,Benjamin; Young, Daniel

1990-01-01

A major design and analysis challenge for the JWST ISIM structure is thermal survivability of metal/composite bonded joints below the cryogenic temperature of 30K (-405 F). Current bonded joint concepts include internal invar plug fittings, external saddle titanium/invar fittings and composite gusset/clip joints all bonded to M55J/954-6 and T300/954-6 hybrid composite tubes (75mm square). Analytical experience and design work done on metal/composite bonded joints at temperatures below that of liquid nitrogen are limited and important analysis tools, material properties, and failure criteria for composites at cryogenic temperatures are sparse in the literature. Increasing this challenge is the difficulty in testing for these required tools and properties at cryogenic temperatures. To gain confidence in analyzing and designing the ISIM joints, a comprehensive joint development test program has been planned and is currently running. The test program is designed to produce required analytical tools and develop a composite failure criterion for bonded joint strengths at cryogenic temperatures. Finite element analysis is used to design simple test coupons that simulate anticipated stress states in the flight joints; subsequently the test results are used to correlate the analysis technique for the final design of the bonded joints. In this work, we present an overview of the analysis and test methodology, current results, and working joint designs based on developed techniques and properties.

Influence of ultraviolet irradiation treatment on porcelain bond strength of titanium surfaces.

PubMed

Kumasaka, Tomonari; Ohno, Akinori; Hori, Norio; Hoshi, Noriyuki; Maruo, Katsuichiro; Kuwabara, Atsushi; Seimiya, Kazuhide; Toyoda, Minoru; Kimoto, Katsuhiko

2018-01-26

To determine the effect of titanium (Ti) surface modification by ultraviolet irradiation (UVI) on the bond strength between Ti and porcelain. Grade 2 Ti plates were allotted to five groups: sandblasted (SA), 15 min UVI (UV), SA+5 min UVI (SA+UV5), SA+10 min UVI (SA+UV10), and SA+15 min UVI (SA+UV15). After surface treatment, porcelain was added. A precious metal (MC) was used for comparison with Ti. The effects of 24-h storage at room temperature versus thermal cycling only at 5 and 55°C in water were evaluated. Subsequently, the tensile strength of each sample was tested. Data were analyzed using one-way analysis of variance and the Tukey test. In both the room temperature and thermal cycling groups, the MC and SA+15 min UVI samples showed significantly greater bond strengths than the other samples (p<0.05). UVI processing efficiently increases the bond strength between porcelain and the Ti surface.

Molecular dynamics simulations and CD spectroscopy reveal hydration-induced unfolding of the intrinsically disordered LEA proteins COR15A and COR15B from Arabidopsis thaliana.

PubMed

Navarro-Retamal, Carlos; Bremer, Anne; Alzate-Morales, Jans; Caballero, Julio; Hincha, Dirk K; González, Wendy; Thalhammer, Anja

2016-10-07

The LEA (late embryogenesis abundant) proteins COR15A and COR15B from Arabidopsis thaliana are intrinsically disordered under fully hydrated conditions, but obtain α-helical structure during dehydration, which is reversible upon rehydration. To understand this unusual structural transition, both proteins were investigated by circular dichroism (CD) and molecular dynamics (MD) approaches. MD simulations showed unfolding of the proteins in water, in agreement with CD data obtained with both HIS-tagged and untagged recombinant proteins. Mainly intramolecular hydrogen bonds (H-bonds) formed by the protein backbone were replaced by H-bonds with water molecules. As COR15 proteins function in vivo as protectants in leaves partially dehydrated by freezing, unfolding was further assessed under crowded conditions. Glycerol reduced (40%) or prevented (100%) unfolding during MD simulations, in agreement with CD spectroscopy results. H-bonding analysis indicated that preferential exclusion of glycerol from the protein backbone increased stability of the folded state.

Shear-bond-strength of orthodontic brackets to aged nano-hybrid composite-resin surfaces using different surface preparation.

PubMed

Demirtas, Hatice Kubra; Akin, Mehmet; Ileri, Zehra; Basciftci, Faruk Ayhan

2015-01-01

The aim of this study was to evaluate the effects of different surface preparation methods on the shear bond strength (SBS) of orthodontic metal brackets to aged nano-hybrid resin composite surfaces in vitro. A total of 100 restorative composite resin discs, 6 mm in diameter and 3 mm thick, were obtained and treated with an ageing procedure. After ageing, the samples were randomly divided as follows according to surface preparation methods: (1)Control, (2)37% phosphoric acid gel, (3)Sandblasting, (4)Diamond bur, (5)Air-flow and 20 central incisor teeth were used for the control etched group. SBS test were applied on bonded metal brackets to all samples. SBS values and residual adhesives were evaluated. Analysis of variance showed a significant difference (p<0.001) between the groups. Sandblasted group had the highest SBS value (12.85 MPa) in experimental groups. The sandblasting surface treatment is recommended as an effective method of bonding orthodontic metal brackets to nano-hybrid composite resin surfaces.

Market-implied spread for earthquake CAT bonds: financial implications of engineering decisions.

PubMed

Damnjanovic, Ivan; Aslan, Zafer; Mander, John

2010-12-01

In the event of natural and man-made disasters, owners of large-scale infrastructure facilities (assets) need contingency plans to effectively restore the operations within the acceptable timescales. Traditionally, the insurance sector provides the coverage against potential losses. However, there are many problems associated with this traditional approach to risk transfer including counterparty risk and litigation. Recently, a number of innovative risk mitigation methods, termed alternative risk transfer (ART) methods, have been introduced to address these problems. One of the most important ART methods is catastrophe (CAT) bonds. The objective of this article is to develop an integrative model that links engineering design parameters with financial indicators including spread and bond rating. The developed framework is based on a four-step structural loss model and transformed survival model to determine expected excess returns. We illustrate the framework for a seismically designed bridge using two unique CAT bond contracts. The results show a nonlinear relationship between engineering design parameters and market-implied spread. © 2010 Society for Risk Analysis.

Synthesis, crystal structure, antimicrobial activity and DNA-binding of hydrogen-bonded proton-transfer complex of 2,6-diaminopyridine with picric acid.

PubMed

Khan, Ishaat M; Ahmad, Afaq; Ullah, M F

2011-04-04

A proton-transfer (charge transfer) complex formed on the reaction between 2,6-diaminopyridine (donor) and picric acid (acceptor) was synthesized and characterized by FTIR, (1)H NMR, thermal and elemental analysis. The crystal structure determined by single-crystal X-ray diffraction indicates that cation and anion are joined together by strong N(+)-H- -O(-) type hydrogen bonds. The hydrogen-bonded charge transfer (HBCT) complex was screened for its pharmacology such as antimicrobial activity against various fungal and bacterial strains and Calf thymus DNA-binding. The results showed that HBCT complex (100μg/ml) exhibited good antibacterial antifungal activity as that of standard antibiotics Tetracycline and Nystatin. A molecular frame work through H-bonding interactions between neighboring moieties is found to be responsible for high melting point of resulting complex. This has been attributed to the formation of 1:1 HBCT complex. Copyright © 2011 Elsevier B.V. All rights reserved.

Modeling dental composite shrinkage by digital image correlation and finite element methods

NASA Astrophysics Data System (ADS)

Chen, Terry Yuan-Fang; Huang, Pin-Sheng; Chuang, Shu-Fen

2014-10-01

Dental composites are light-curable resin-based materials with an inherent defect of polymerization shrinkage which may cause tooth deflection and debonding of restorations. This study aimed to combine digital image correlation (DIC) and finite element analysis (FEA) to model the shrinkage behaviors under different light curing regimens. Extracted human molars were prepared with proximal cavities for composite restorations, and then divided into three groups to receive different light curing protocols: regular intensity, low intensity, and step-curing consisting of low and high intensities. For each tooth, the composite fillings were consecutively placed under both unbonded and bonded conditions. At first, the shrinkage of the unbonded restorations was analyzed by DIC and adopted as the setting of FEA. The simulated shrinkage behaviors obtained from FEA were further validated by the measurements in the bonded cases. The results showed that different light curing regimens affected the shrinkage in unbonded restorations, with regular intensity showing the greatest shrinkage strain on the top surface. The shrinkage centers in the bonded cases were located closer to the cavity floor than those in the unbonded cases, and were less affected by curing regimens. The FEA results showed that the stress was modulated by the accumulated light energy density, while step-curing may alleviate the tensile stress along the cavity walls. In this study, DIC provides a complete description of the polymerization shrinkage behaviors of dental composites, which may facilitate the stress analysis in the numerical investigation.

Analysis of local bond-orientational order for liquid gallium at ambient pressure: Two types of cluster structures.

PubMed

Chen, Lin-Yuan; Tang, Ping-Han; Wu, Ten-Ming

2016-07-14

In terms of the local bond-orientational order (LBOO) parameters, a cluster approach to analyze local structures of simple liquids was developed. In this approach, a cluster is defined as a combination of neighboring seeds having at least nb local-orientational bonds and their nearest neighbors, and a cluster ensemble is a collection of clusters with a specified nb and number of seeds ns. This cluster analysis was applied to investigate the microscopic structures of liquid Ga at ambient pressure (AP). The liquid structures studied were generated through ab initio molecular dynamics simulations. By scrutinizing the static structure factors (SSFs) of cluster ensembles with different combinations of nb and ns, we found that liquid Ga at AP contained two types of cluster structures, one characterized by sixfold orientational symmetry and the other showing fourfold orientational symmetry. The SSFs of cluster structures with sixfold orientational symmetry were akin to the SSF of a hard-sphere fluid. On the contrary, the SSFs of cluster structures showing fourfold orientational symmetry behaved similarly as the anomalous SSF of liquid Ga at AP, which is well known for exhibiting a high-q shoulder. The local structures of a highly LBOO cluster whose SSF displayed a high-q shoulder were found to be more similar to the structure of β-Ga than those of other solid phases of Ga. More generally, the cluster structures showing fourfold orientational symmetry have an inclination to resemble more to β-Ga.

Superplastic Forming/Diffusion Bonding Without Interlayer of 5A90 Al-Li Alloy Hollow Double-Layer Structure

NASA Astrophysics Data System (ADS)

Jiang, Shaosong; Jia, Yong; Lu, Zhen; Shi, Chengcheng; Zhang, Kaifeng

2017-09-01

The hollow double-layer structure of 5A90 Al-Li alloy was fabricated by SPF/DB process in this study. The characteristics and mechanism of 5A90 Al-Li alloy with respect to superplasticity and diffusion bonding were investigated. Tensile tests showed that the optimal elongation of tensile specimens was 243.97% at the temperature of 400 °C and the strain rate of 0.001 s-1. Effect of the surface roughness, bonding temperature and bonding time to determine the microstructure and mechanical properties of diffusion bonding joints was investigated, and the optimum bonding parameters were 540 °C/2.5 h/Ra18. Through the finite element simulation, it could be found that the SPF/DB process of hollow double-layer structure was feasible. The hollow double-layer structure of 5A90 Al-Li alloy was manufactured, showing that the thickness distribution of the bonding area was uniform and the thinnest part was the round corner. The SEM images of diffusion bonding joints showed that sound bonding interfaces were obtained in which no discontinuity existed.

Microstructure and mechanical properties of diffusion bonded W/steel joint using V/Ni composite interlayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, W.S.; Cai, Q.S., E-mail: cai2009pm@163.com; Ma, Y.Z.

2013-12-15

Diffusion bonding between W and steel using V/Ni composite interlayer was carried out in vacuum at 1050 °C and 10 MPa for 1 h. The microstructural examination and mechanical property evaluation of the joints show that the bonding of W to steel was successful. No intermetallic compound was observed at the steel/Ni and V/W interfaces for the joints bonded. The electron probe microanalysis and X-ray diffraction analysis revealed that Ni{sub 3}V, Ni{sub 2}V, Ni{sub 2}V{sub 3} and NiV{sub 3} were formed at the Ni/V interface. The tensile strength of about 362 MPa was obtained for as-bonded W/steel joint and themore » failure occurred at W near the V/W interface. The nano-indentation test across the joining interfaces demonstrated the effect of solid solution strengthening and intermetallic compound formation in the diffusion zone. - Highlights: • Diffusion bonding of W to steel was realized using V/Ni composite interlayer. • The interfacial microstructure of the joint was clarified. • Several V–Ni intermetallic compounds were formed in the interface region. • The application of V/Ni composite interlayer improved the joining quality.« less

Spectral characterization, cyclic voltammetry, morphology, biological activities and DNA cleaving studies of amino acid Schiff base metal(II) complexes

NASA Astrophysics Data System (ADS)

Neelakantan, M. A.; Rusalraj, F.; Dharmaraja, J.; Johnsonraja, S.; Jeyakumar, T.; Sankaranarayana Pillai, M.

2008-12-01

Metal complexes are synthesized with Schiff bases derived from o-phthalaldehyde (opa) and amino acids viz., glycine (gly) L-alanine (ala), L-phenylalanine (pal). Metal ions coordinate in a tetradentate or hexadentate manner with these N 2O 2 donor ligands, which are characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic, 1H NMR and EPR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Based on EPR studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values calculated for copper complexes at 300 K and in frozen DMSO (77 K) indicate the presence of the unpaired electron in the d orbital. The evaluated metal-ligand bonding parameters showed strong in-plane σ- and π-bonding. X-ray diffraction (XRD) and scanning electron micrography (SEM) analysis provide the crystalline nature and the morphology of the metal complexes. The cyclic voltammograms of the Cu(II)/Mn(II)/VO(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5 V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions. The biological activity of the complexes has been tested on eight bacteria and three fungi. Cu(II) and Ni(II) complexes show an increased activity in comparison to the controls. The metal complexes of opapal Schiff base were evaluated for their DNA cleaving activities with calf-thymus DNA (CT DNA) under aerobic conditions. Cu(II) and VO(II) complexes show more pronounced activity in presence of the oxidant.

[Antibacterial effect of self-etching adhesive systems on Streptococcus mutans].

PubMed

Zhang, Lu; Yuan, Chong-yang; Tian, Fu-cong; Wang, Xiao-yan; Gao, Xue-jun

2016-02-18

To investigate the antibacterial effect of different self-etching adhesive systems against Streptococcus mutans (S. mutans). Six reagents Clearfil(TM) SE Bond primer (SP), Clearfil(TM) SE Bond adhesive (SA),Clearfil(TM) Protect Bond primer (PP), which contained antibacterial monomer methacryloyloxydodecylpyridinium bromide (MDPB), ClearfilTM Protect Bond adhesive (PA), positive control chlorhexidine acetate [CHX, 1% (mass fraction)], and negative control phosphate buffer solution (PBS) were selected. They were mixed with S. mutans for 30 s respectively, then colony-forming units (CFU) were counted after incubated for 48 h on brain heart infusion (BHI) agar medium. The 6 reagents were applied to the sterile paper discs, and distributed onto the BHI agar medium with S. mutans and incubated for 24 h, then the inhibition zones were observed. CHX, PBS, PP, and SP were added on the dentin with artificial caries induced by S. mutans and kept for 30 s, then confocal laser scanning microscope (CLSM) was used to observe the live and dead bacteria after staining. The ratio of live to dead bacteria was calculated. PP+PA and SP+SA were applied on the dentin according to the manual and light cured. S. mutans were incubated on the samples for 2 h, ultrasonically treated and incubated on BHI agar medium for 48 h, then CFU was counted. The data were analyzed by non-parametric analysis and one-way ANOVA. Compared with PBS, the PP, SP, PA, SA and CHX showed the antibacterial effect on free S. mutans (P<0.05); SP and PP showed stronger antibacterial effect than PA, SA and CHX (P<0.05). CHX, SP and PP presented inhibition zones, while PBS, SA and PA did not. Compared with PBS, the CHX, SP and PP could lower the ratio of the live to dead bacteria significantly (P<0.05). Cured self-etching adhesive systems did not show any antibacterial effect on the free S. mutans. The primer of self-etching adhesives Clearfil(TM) SE Bond and Clearfil(TM) Protect Bond showed significant antibacterial effect on free and attached S. mutans. The adhesive only showed antibacterial effect on free S. mutans before light-cured polymerization. After being cured, the self-etching adhesive systems did not show antibacterial effect anymore.

Atomic and molecular analysis highlights the biophysics of unprotonated and protonated retinal in UV and scotopic vision.

PubMed

Kubli-Garfias, Carlos; Vázquez-Ramírez, Ricardo; Cabrera-Vivas, Blanca M; Gómez-Reyes, Baldomero; Ramírez, Juan Carlos

2015-09-26

During the photoreaction of rhodopsin, retinal isomerizes, rotating the C11[double bond, length as m-dash]C12 π-bond from cis to an all-trans configuration. Unprotonated (UR) or protonated (PR) retinal in the Schiff's base (SB) is related to UV and light vision. Because the UR and PR have important differences in their physicochemical reactivities, we compared the atomic and molecular properties of these molecules using DFT calculations. The C10-C11[double bond, length as m-dash]C12-C13 dihedral angle was rotated from 0° to 180° in 45° steps, giving five conformers, and the following were calculated from them: atomic orbital (AO) contributions to the HOMO and LUMO, atomic charges, bond length, bond order, HOMO, LUMO, hardness, electronegativity, polarizability, electrostatic potential, UV-vis spectra and dipole moment (DM). Similarly, the following were analyzed: the energy profile, hybridization, pyramidalization and the hydrogen-out-of-plane (HOOP) wagging from the H11-C11[double bond, length as m-dash]C12-H12 dihedral angle. In addition, retinal with a water H-bond (HR) in the SB was included for comparison. Interestingly, in the PR, C11 and C12 are totally the LUMO and the HOMO, respectively, and have a large electronegativity difference, which predicts an electron jump in these atoms during photoexcitation. At the same time, the PR showed a longer bond length and lower bond order, with a larger DM, lower HOMO-LUMO gap, lower hardness and higher electronegativity. In addition, the AOs of -45° and -90° conformers changed significantly, from pz to py, during the rotation concomitantly with marked hybridization, smooth pyramidalization and lower HOOP activity. Clearly, the atomic and molecular differences between the UR and PR are overwhelming, including the rotational energy profile and light absorption spectra, which indicates that light absorption of UR and PR is already determined by the retinal characteristics of the SB protonation. The HR-model compared with UR shows a lower energy barrier and a discreet bathochromic effect in the UV region.

Silicone Disclosing Material used after Ceramic Surface Treatment Reduces Bond Strength.

PubMed

Fraga, Sara; Oliveira, Sara Cioccari; Pereira, Gabriel Kalil Rocha; Beekman, Pieter; Rippe, Marília Pivetta; Kleverlaan, Cornelis J

To evaluate the effect of a silicone disclosing procedure performed at different timepoints on the shear bond strength (SBS) of cements (self-adhesive composite cement, self-etch composite cement, resin-reinforced glass-ionomer cement) to different substrates (zirconia, lithium disilicate, bovine dentin). The substrate/cement combinations were assigned to two groups (n = 15) according to the timepoint, at which the vinyl polyether silicone disclosing agent was applied: after (experimental groups, EXP) or before (control groups, CTRL) specific micromechanical treatments of the substrate surface. To increase standardization, the cements were applied into rubber rings (2.2 mm diameter x 1.0 mm thickness) positioned on the substrate surface. After luting procedures, all specimens were stored in 37°C distilled water for 24 h, then subjected to SBS testing using a wire loop of 0.2 mm diameter at a crosshead speed of 1 mm/min until failure. Failure analysis was performed for all tested specimens. SBS data were submitted to Weibull analysis. The silicone disclosing procedure performed after micromechanical surface treatment reduced the characteristic shear bond strength to zirconia and lithium disilicate when compared to CTRL. However, for dentin specimens, there was no significant difference between CTRL and EXP for any of the cements investigated. Failure analysis showed a predominance of interfacial failures. The silicone disclosing procedure performed after the micromechanical treatment of ceramic surfaces negatively affected the cement bond strength. Therefore, after using it to check the fit of a prosthesis, clinicians should carefully clean the ceramic surface.

The Effect of Different Chemical Surface Treatments of Denture Teeth on Shear Bond Strength: A Comparative Study

PubMed Central

Palekar, Umesh; Awinashe, Vaibav; Mishra, Sunil Kumar; Kawadkar, Abhishek; Rahangdale, Tripti

2014-01-01

Background: The development of better cross linked acrylic resin teeth has solved the problems related to wearing and discoloration of acrylic teeth. The same cross linking at ridge lap region acts as a double edge sword as it weakens the bond between denture base and tooth. Aim of Study: The purpose of study was to evaluate the effect of surface treatment on the bond strength of resin teeth to denture base resin using monomethyl methacrylate monomer and dichloromethane with no surface treatment acting as control. Settings and Design:Denture base cylinder samples in wax (n=180) were made with maxillary central incisor attached at 450 (JIST 6506). These samples were randomly and equally divided into three groups of 60 each. These specimens were then flasked, dewaxed as per the standard protocol. Materials and Methods: Before acrylization, ridge lap area was treated as follows: Group A- no surface treatment act as control, Group B treated with monomethyl methacrylate monomer, Group C treated with dichloromethane. Digitally controlled acryliser was used for acrylization as per manufacturer’s instructions and shear bond strength was tested on Universal Testing Machine (Servo Hydraulic, 50kN High Strain, BISS Research). Statistical Analysis used: Result was statistically analyzed with One-way analysis of variance (ANOVA) and Post-hoc ANOVA Tukey’s HSD test at 5% level of significance. Results: The application of dichloromethane showed increased bond strength between cross linked acrylic resin teeth and heat cure denture base resin followed by monomethyl methacrylate monomer and control group. Conclusion: The application of dichloromethane on the ridge lap surface of the resin teeth before packing of the dough into the mold significantly increased the bond strength between cross linked acrylic resin teeth and heat cure denture base resin. PMID:25121057

Effect of chlorhexidine and ethanol on the durability of the adhesion of the fiber post relined with resin composite to the root canal.

PubMed

Cecchin, Doglas; de Almeida, José Flávio Affonso; Gomes, Brenda P F A; Zaia, Alexandre Augusto; Ferraz, Caio Cesar Randi

2011-05-01

The aim of this study was to investigate the effects of pretreatment of gel chlorhexidine and ethanol on the bond strength and durability of the adhesion of the fiber post relined with resin composite to the root dentin. Sixty bovine incisor roots were divided into four groups: irrigation with physiologic solution (control), 5 minutes with chlorhexidine, 1 minute with ethanol, and 5 minutes with chlorhexidine followed by 1 minute with ethanol. Fiber posts relined with resin composite were cemented with RelyX ARC (3M ESPE, St Paul, MN) and a self-etching adhesive system Clearfil SE Bond (Kuraray, Kurashiki, Japan). Each group was randomly divided into three subgroups: 24 hours of water storage, 12 months of water storage, and 12 months of oil storage. All roots were sectioned transversely in the coronal, middle, and apical regions, producing 1-mm thick slices, and the push-out test was performed. Statistical analysis was performed using analysis of variance and the Tukey test for post hoc comparisons (α = 0.05). Immediate groups showed similar bond strength values with or without chlorhexidine and/or ethanol pretreatment (P > .05). A significant decrease in the bond strength in the control group was observed after 12 months of storage in water and oil (P < .05). The use of chlorhexidine- and/or ethanol-preserved bond strength in the groups stored in water and oil for 12 months (P < .05). Chlorhexidine and/or ethanol pretreatment were capable of preserving the bond strength of the fiber post relined with resin composite to root dentin for 12 months. Copyright © 2011 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Statistical analysis of native contact formation in the folding of designed model proteins

NASA Astrophysics Data System (ADS)

Tiana, Guido; Broglia, Ricardo A.

2001-02-01

The time evolution of the formation probability of native bonds has been studied for designed sequences which fold fast into the native conformation. From this analysis a clear hierarchy of bonds emerge: (a) local, fast forming highly stable native bonds built by some of the most strongly interacting amino acids of the protein; (b) nonlocal bonds formed late in the folding process, in coincidence with the folding nucleus, and involving essentially the same strongly interacting amino acids already participating in the fast bonds; (c) the rest of the native bonds whose behavior is subordinated, to a large extent, to that of the strong local and nonlocal native contacts.

The effect of coating patterns with spinel-based investment on the castability and porosity of titanium cast into three phosphate-bonded investments.

PubMed

Pieralini, Anelise R F; Benjamin, Camila M; Ribeiro, Ricardo Faria; Scaf, Gulnara; Adabo, Gelson Luis

2010-10-01

This study evaluated the effect of pattern coating with spinel-based investment Rematitan Ultra (RU) on the castability and internal porosity of commercially pure (CP) titanium invested into phosphate-bonded investments. The apparent porosity of the investment was also measured. Square patterns (15 × 15 × 0.3 mm(3)) were either coated with RU, or not and invested into the phosphate-bonded investments: Rematitan Plus (RP), Rema Exakt (RE), Castorit Super C (CA), and RU (control group). The castings were made in an Ar-arc vacuum-pressure machine. The castability area (mm(2) ) was measured by an image-analysis system (n = 10). For internal porosity, the casting (12 × 12 × 2 mm(3) ) was studied by the X-ray method, and the projected porous area percentage was measured by an image-analysis system (n = 10). The apparent porosity of the investment (n = 10) was measured in accordance with the ASTM C373-88 standard. Analysis of variance (One-way ANOVA) of castability was significant, and the Tukey test indicated that RU had the highest mean but the investing technique with coating increased the castability for all phosphate-bonded investments. The analysis of the internal porosity of the cast by the nonparametric test demonstrated that the RP, RE, and CA with coating and RP without coating did not differ from the control group (RU), while the CA and RE casts without coating were more porous. The one-way ANOVA of apparent porosity of the investment was significant, and the Tukey test showed that the means of RU (36.10%) and CA (37.22%) were higher than those of RP (25.91%) and RE (26.02%). Pattern coating with spinel-based material prior to phosphate-bonded investments can influence the castability and the internal porosity of CP Ti. © 2010 by The American College of Prosthodontists.

Microshear Bond Strength of OptiBond All-in-One Self-adhesive Agent to Er:YAG Laser Treated Enamel After Thermocycling and Water Storage.

PubMed

Kasraei, Shahin; Yarmohammadi, Ebrahim; Ghazizadeh, Mohammad Vahid

2016-01-01

Introduction: This study aimed to compare the microshear bond strength of composite to enamel treated with Erbium-Doped Yttrium Aluminum Garnet (Er:YAG) laser using a self-etch one step bonding agent. Methods: Seventy-six enamel surfaces were prepared from 38 sound human third molar teeth. Specimens were randomly divided into four groups of 18. The enamel surface in half the specimens was irradiated with Er:YAG laser. One extra specimen from each group was evaluated under a scanning electron microscope (SEM). Composite micro-cylinders were bonded to the specimen surfaces using OptiBond All-In-One (OB) adhesive agent and stored in distilled water for 24 hours. Half the specimens were thermocycled (2000 cycles) and stored in distilled water at 37°C for three months (TW). The microshear bond strength of composite to enamel was measured using a universal testing machine at a crosshead speed of 1 mm/min. The fractured surfaces were evaluated under a stereomicroscope at ×40 magnification to determine the mode of failure. Data were analyzed using repeated measures analysis of variance (ANOVA) and t test. Results: The mean values (±standard deviation) were 17.96 ± 2.92 MPa in OB group, 22.29 ± 4.25 MPa in laser + OB group, 18.11 ± 3.52 MPa in laser + OB + TW group and 9.42 ± 2.47 MPa in OB + TW group. Repeated measures ANOVA showed that laser irradiation increased the microshear bond strength ( P < 0.001). Bond strength decreased when the samples were thermocycled and stored for three months ( P < 0.001). The interaction effect of water storage and laser treatment on bond strength was significant ( P < 0.05). Conclusion: Enamel surface preparation with Er:YAG laser is recommended to enhance the durability of the bond of self-etch bonding systems to enamel.

Microshear Bond Strength of OptiBond All-in-One Self-adhesive Agent to Er:YAG Laser Treated Enamel After Thermocycling and Water Storage

PubMed Central

Kasraei, Shahin; Yarmohammadi, Ebrahim; Ghazizadeh, Mohammad Vahid

2016-01-01

Introduction: This study aimed to compare the microshear bond strength of composite to enamel treated with Erbium-Doped Yttrium Aluminum Garnet (Er:YAG) laser using a self-etch one step bonding agent. Methods: Seventy-six enamel surfaces were prepared from 38 sound human third molar teeth. Specimens were randomly divided into four groups of 18. The enamel surface in half the specimens was irradiated with Er:YAG laser. One extra specimen from each group was evaluated under a scanning electron microscope (SEM). Composite micro-cylinders were bonded to the specimen surfaces using OptiBond All-In-One (OB) adhesive agent and stored in distilled water for 24 hours. Half the specimens were thermocycled (2000 cycles) and stored in distilled water at 37°C for three months (TW). The microshear bond strength of composite to enamel was measured using a universal testing machine at a crosshead speed of 1 mm/min. The fractured surfaces were evaluated under a stereomicroscope at ×40 magnification to determine the mode of failure. Data were analyzed using repeated measures analysis of variance (ANOVA) and t test. Results: The mean values (±standard deviation) were 17.96 ± 2.92 MPa in OB group, 22.29 ± 4.25 MPa in laser + OB group, 18.11 ± 3.52 MPa in laser + OB + TW group and 9.42 ± 2.47 MPa in OB + TW group. Repeated measures ANOVA showed that laser irradiation increased the microshear bond strength (P < 0.001). Bond strength decreased when the samples were thermocycled and stored for three months (P < 0.001). The interaction effect of water storage and laser treatment on bond strength was significant (P < 0.05). Conclusion: Enamel surface preparation with Er:YAG laser is recommended to enhance the durability of the bond of self-etch bonding systems to enamel. PMID:28144434

Spectroscopic investigation, vibrational assignments, HOMO-LUMO, NBO, MEP analysis and molecular docking studies of oxoaporphine alkaloid liriodenine

NASA Astrophysics Data System (ADS)

Costa, Renyer A.; Pitt, Priscilla Olliveira; Pinheiro, Maria Lucia B.; Oliveira, Kelson M. T.; Salomé, Kahlil Schwanka; Barison, Andersson; Costa, Emmanoel Vilaça

2017-03-01

A combined experimental and theoretical DFT study of the structural, vibrational and electronic properties of liriodenine is presented using B3LYP function with 6-311G (2d, p) basis set. The theoretical geometry optimization data were compared with the X-ray data for a similar structure in the associated literature, showing similar values. In addition, natural bond orbitals (NBOs), HOMO-LUMO energy gap, mapped molecular Electrostatic Potential (MEP) surface calculation, first and second order hyperpolarizabilities were also performed with the same calculation level. Theoretical UV spectrum agreed well with the measured experimental data, with transitions assigned. The molecular electrostatic potential map shows opposite potentials regions that forms hydrogen bonds that stabilize the dimeric form, which were confirmed by the close values related to the C dbnd O bond stretching between the dimeric form and the experimental IR spectra (1654 cm- 1 for the experimental, 1700 cm- 1 for the dimer form). Calculated HOMO/LUMO gaps shows the excitation energy for Liriodenine, justifying its stability and kinetics reaction. Molecular docking studies with Candida albicans dihydrofolate reductase (DHFR) and Candida albicans secreted aspartic protease (SAP) showed binding free energies values of - 8.5 and - 8.3 kcal/mol, suggesting good affinity between the liriodenine and the target macromolecules.

Integrity of production wells and confining unit at the Naval Weapons Industrial Reserve Plant, Dallas, Texas, 1995

USGS Publications Warehouse

Jones, Sonya A.; Paillet, Frederick L.

1997-01-01

The results of borehole geophysical log analysis indicate that two of the production wells could have vertically connected intervals where cement bonding in the well annulus is poor. The other production wells have overall good bonding. Temperature logs do not indicate flow behind casing except in the screened interval of one well. Geophysical logs show the Eagle Ford Shale ranges from 147 to 185 feet thick at the site. The Eagle Ford Shale has low permeability and a high plasticity index. These physical characteristics make the Eagle Ford Shale an excellent confining unit.

Sub-ablative Er,Cr:YSGG laser irradiation under all-ceramic restorations: effects on demineralization and shear bond strength.

PubMed

Bağlar, Serdar

2018-01-01

This study evaluated the caries resistant effects of sub-ablative Er,Cr:YSGG laser irradiation alone and combined with fluoride in comparison with fluoride application alone on enamel prepared for veneer restorations. And also, evaluated these treatments' effects on the shear bond strength of all-ceramic veneer restorations. One hundred and thirty-five human maxillary central teeth were assigned to groups of 1a-control, 1b-laser treated, 1c-fluoride treated, 1d-laser + fluoride treated for shear bond testing and to groups of 2a-positive control(non-demineralised), 2b-laser treated, 2c-fluoride treated, 2d-laser + fluoride treated, 2e-negative control (demineralised) for microhardness testing (n = 15, N = 135). Demineralisation solutions of microhardness measurements were used for the ICP-OES elemental analysis. The parameters for laser irradiation were as follows: power output, 0.25 W; total energy density, 62.5 J/cm 2 and energy density per pulse, 4.48 J/cm 2 with an irradiation time of 20 s and with no water cooling. Five percent NaF varnish was used as fluoride preparate. ANOVA and Tukey HSD tests were performed (α = 5%). Surface treatments showed no significant effects on shear bond strength values (p = 0.579). However, significant differences were found in microhardness measurements and in elemental analysis of Ca and P amounts (p < 0.01). Surface-treated groups showed significantly high VNH values and significantly low ICP-OES values when compared with non-treated (-control) group while there were no significance among surface-treated groups regarding VHN and ICP-OES values. Sub-ablative Er,Cr:YSGG treatment alone or combined with fluoride is as an effective method as at least fluoride alone for preventing the prepared enamel to demineralization with no negative effect on shear bond strength.

Thieno[3,2-c]pyran-4-one based novel small molecules: their synthesis, crystal structure analysis and in vitro evaluation as potential anticancer agents.

PubMed

Nakhi, Ali; Adepu, Raju; Rambabu, D; Kishore, Ravada; Vanaja, G R; Kalle, Arunasree M; Pal, Manojit

2012-07-01

Novel thieno[3,2-c]pyran-4-one based small molecules were designed as potential anticancer agents. Expeditious synthesis of these compounds was carried out via a multi-step sequence consisting of few steps such as Gewald reaction, Sandmeyer type iodination, Sonogashira type coupling followed by iodocyclization and then Pd-mediated various C-C bond forming reactions. The overall strategy involved the construction of thiophene ring followed by the fused pyranone moiety and then functionalization at C-7 position of the resultant thieno[3,2-c]pyran-4-one framework. Some of the compounds synthesized showed selective growth inhibition of cancer cells in vitro among which two compounds for example, 5d and 6c showed IC(50) values in the range of 2.0-2.5 μM. The crystal structure analysis of an active compound along with hydrogen bonding patterns and molecular arrangement present within the molecule is described. Copyright © 2012 Elsevier Ltd. All rights reserved.

Analysis of biological time-lapse microscopic experiment from the point of view of the information theory.

PubMed

Štys, Dalibor; Urban, Jan; Vaněk, Jan; Císař, Petr

2011-06-01

We report objective analysis of information in the microscopic image of the cell monolayer. The process of transfer of information about the cell by the microscope is analyzed in terms of the classical Shannon information transfer scheme. The information source is the biological object, the information transfer channel is the whole microscope including the camera chip. The destination is the model of biological system. The information contribution is analyzed as information carried by a point to overall information in the image. Subsequently we obtain information reflection of the biological object. This is transformed in the biological model which, in information terminology, is the destination. This, we propose, should be constructed as state transitions in individual cells modulated by information bonds between the cells. We show examples of detected cell states in multidimensional state space. This space is reflected as colour channel intensity phenomenological state space. We have also observed information bonds and show examples of them.

Analysis of biological time-lapse microscopic experiment from the point of view of the information theory.

PubMed

Stys, Dalibor; Urban, Jan; Vanek, Jan; Císar, Petr

2010-07-01

We report objective analysis of information in the microscopic image of the cell monolayer. The process of transfer of information about the cell by the microscope is analyzed in terms of the classical Shannon information transfer scheme. The information source is the biological object, the information transfer channel is the whole microscope including the camera chip. The destination is the model of biological system. The information contribution is analyzed as information carried by a point to overall information in the image. Subsequently we obtain information reflection of the biological object. This is transformed in the biological model which, in information terminology, is the destination. This, we propose, should be constructed as state transitions in individual cells modulated by information bonds between the cells. We show examples of detected cell states in multidimensional state space reflected in space an colour channel intensity phenomenological state space. We have also observed information bonds and show examples of them. Copyright 2010 Elsevier Ltd. All rights reserved.

Synthesis, characterization, AIM and NBO analysis of HMX/DMI cocrystal explosive

NASA Astrophysics Data System (ADS)

Lin, He; Zhu, Shun-Guan; Li, Hong-Zhen; Peng, Xin-Hua

2013-09-01

1,3,5,7-Tetranitro-1,3,5,7-tetrazacyclooctane (HMX)/1,3-dimethyl-2-imidazolidinone (DMI) cocrystal explosive was synthesized and characterized by using X-ray single crystal diffraction. HMX/DMI cocrystal crystallizes in the monoclinic system (space group Cm), with cell parameters a = 7.231(2)Å, b = 14.739(2)Å, c = 7.552(1)Å, β = 96.66°. In addition, density functional theory, involving binding energy, natural bond orbital (NBO) analysis, atoms in molecule (AIM) analysis, band structure, and density of states, was adopted to investigate intermolecular interactions for the formation of HMX/DMI cocrystal. The results show that hydrogen bondings between methylene groups of HMX molecules and O atoms of DMI molecules are the main intermolecular interactions. This research provides the basis for further design of cocrystal explosives, which are composed of HMX and energetic materials.

Characterizing Bonding Patterns in Diradicals and Triradicals by Density-Based Wave Function Analysis: A Uniform Approach.

PubMed

Orms, Natalie; Rehn, Dirk R; Dreuw, Andreas; Krylov, Anna I

2018-02-13

Density-based wave function analysis enables unambiguous comparisons of the electronic structure computed by different methods and removes ambiguity of orbital choices. We use this tool to investigate the performance of different spin-flip methods for several prototypical diradicals and triradicals. In contrast to previous calibration studies that focused on energy gaps between high- and low spin-states, we focus on the properties of the underlying wave functions, such as the number of effectively unpaired electrons. Comparison of different density functional and wave function theory results provides insight into the performance of the different methods when applied to strongly correlated systems such as polyradicals. We show that canonical molecular orbitals for species like large copper-containing diradicals fail to correctly represent the underlying electronic structure due to highly non-Koopmans character, while density-based analysis of the same wave function delivers a clear picture of the bonding pattern.

Comparison of Self-Etch Primers with Conventional Acid Etching System on Orthodontic Brackets

PubMed Central

Zope, Amit; Zope-Khalekar, Yogita; Chitko, Shrikant S.; Kerudi, Veerendra V.; Patil, Harshal Ashok; Jaltare, Pratik; Dolas, Siddhesh G

2016-01-01

Introduction The self-etching primer system consists of etchant and primer dispersed in a single unit. The etching and priming are merged as a single step leading to fewer stages in bonding procedure and reduction in the number of steps that also reduces the chance of introduction of error, resulting in saving time for the clinician. It also results in smaller extent of enamel decalcification. Aim To compare the Shear Bond Strength (SBS) of orthodontic bracket bonded with Self-Etch Primers (SEP) and conventional acid etching system and to study the surface appearance of teeth after debonding; etching with conventional acid etch and self-etch priming, using stereomicroscope. Materials and Methods Five Groups (n=20) were created randomly from a total of 100 extracted premolars. In a control Group A, etching of enamel was done with 37% phosphoric acid and bonding of stainless steel brackets with Transbond XT (3M Unitek, Monrovia, California). Enamel conditioning in left over four Groups was done with self-etching primers and adhesives as follows: Group B-Transbond Plus (3M Unitek), Group C Xeno V+ (Dentsply), Group D-G-Bond (GC), Group E-One-Coat (Coltene). The Adhesive Remnant Index (ARI) score was also evaluated. Additionally, the surface roughness using profilometer were observed. Results Mean SBS of Group A was 18.26±7.5MPa, Group B was 10.93±4.02MPa, Group C was 6.88±2.91MPa while of Group D was 7.78±4.13MPa and Group E was 10.39±5.22MPa respectively. In conventional group ARI scores shows that over half of the adhesive was remaining on the surface of tooth (score 1 to 3). In self-etching primer groups ARI scores show that there was no or minor amount of adhesive remaining on the surface of tooth (score 4 and 5). SEP produces a lesser surface roughness on the enamel than conventional etching. However, statistical analysis shows significant correlation (p<0.001) of bond strength with surface roughness of enamel. Conclusion All groups might show clinically useful SBS values and Transbond XT can be successfully used for bracket bonding after enamel conditioning with any of the SEPs tested. The SEPs used in Groups C (Xeno V+) and D (G-Bond) have significantly lowered SBS. Although, the values might still be clinically acceptable. PMID:28208997

Fractography of interface after microtensile bond strength test using swept-source optical coherence tomography.

PubMed

Dao Luong, Minh Nguyet; Shimada, Yasushi; Turkistani, Alaa; Tagami, Junji; Sumi, Yasunori; Sadr, Alireza

2016-07-01

To determine the effect of crosshead speed and placement technique on interfacial crack formation in microtensile bond strength (MTBS) test using swept-source optical coherence tomography (SS-OCT). MTBS test beams (0.9×0.9mm(2)) were prepared from flat human dentin disks bonded with self-etch adhesive (Clearfil SE Bond, Kuraray) and universal composite (Clearfil AP-X, Kuraray) with or without flowable composite lining (Estelite Flow Quick, Tokuyama). Each beam was scanned under SS-OCT (Santec, Japan) at 1319nm center wavelength before MTBS test was performed at crosshead speed of either 1 or 10mm/min (n=10). The beams were scanned by SS-OCT again to detect and measure cracks at the debonded interface using digital image analysis software. Representative beams were observed under confocal laser scanning microscope to confirm the fractography findings. Two-way ANOVA showed that for MTBS the crosshead speed was not a significant factor (p>0.05), while there was a difference between placement techniques (p<0.001), with flowable lining yielding higher mean values. On the other hand, for crack formation, there was a significant difference between crosshead speeds (p<0.01), while the placement technique did not show up as a statistically significant factor (p>0.05). The interaction of factors were not significant (p>0.05). Testing MTBS samples at higher crosshead speeds induced more cracks in dentin. Lining with a flowable composite improved the bonding quality and increased the bond strength. SS-OCT can visualize interfacial cracks after restoration debonding. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Driving force analysis of proton tunnelling across a reactivity series for an enzyme-substrate complex.

PubMed

Hothi, Parvinder; Hay, Sam; Roujeinikova, Anna; Sutcliffe, Michael J; Lee, Michael; Leys, David; Cullis, Paul M; Scrutton, Nigel S

2008-11-24

Quantitative structure-activity relationships are widely used to probe C-H bond breakage by quinoprotein enzymes. However, we showed recently that p-substituted benzylamines are poor reactivity probes for the quinoprotein aromatic amine dehydrogenase (AADH) because of a requirement for structural change in the enzyme-substrate complex prior to C-H bond breakage. This rearrangement is partially rate limiting, which leads to deflated kinetic isotope effects for p-substituted benzylamines. Here we report reactivity (driving force) studies of AADH with p-substituted phenylethylamines for which the kinetic isotope effect (approximately 16) accompanying C-H/C-(2)H bond breakage is elevated above the semi-classical limit. We show bond breakage occurs by quantum tunnelling and that within the context of the environmentally coupled framework for H-tunnelling the presence of the p-substituent places greater demand on the apparent need for fast promoting motions. The crystal structure of AADH soaked with phenylethylamine or methoxyphenylethylamine indicates that the structural change identified with p-substituted benzylamines should not limit the reaction with p-substituted phenylethylamines. This is consistent with the elevated kinetic isotope effects measured with p-substituted phenylethylamines. We find a good correlation in the rate constant for proton transfer with bond dissociation energy for the reactive C-H bond, consistent with a rate that is limited by a Marcus-like tunnelling mechanism. As the driving force becomes larger, the rate of proton transfer increases while the Marcus activation energy becomes smaller. This is the first experimental report of the driving force perturbation of H-tunnelling in enzymes using a series of related substrates. Our study provides further support for proton tunnelling in AADH.

Timing considerations on the shear bond strength of orthodontic brackets after topical fluoride varnish applications

PubMed Central

Cossellu, Gianguido; Lanteri, Valentina; Butera, Andrea; Laffi, Nicola; Merlini, Alberto; Farronato, Giampietro

2017-01-01

Objectives: To assess the best temporal association between the application of a fluoride varnish on enamel and bonding procedures. Materials and Methods: Eighty mandibular bovine incisors were used. Teeth were divided into 4 groups (20 per group); Groups 1–3 were treated with fluoride varnish (Fluor Protector, Ivoclar Vivadent, Schaan, Liechtenstein), and Group 4 served as control with no pretreatment. Tooth were stored in deionized water (37°C) and subjected to thermal cycling for 400 (Group 1), 800 (Group 2), and 2500 (Group 3) cycles corresponding, respectively, to 15, 30, and 90 days in order to simulate the three different timing of bracket bonding. Shear bond strength (SBS) was measured using an Instron Universal Testing machine. Tooth surfaces were examined under a stereomicroscope at 10× magnification to assess the amount of adhesive remnant index (ARI). One-way analysis of variance (ANOVA) and Tukey's honestly significant difference post-hoc test were used for the comparison of SBS values between groups (P < 0.05). The Chi-square test was used to examine differences among ARI scores. (P < 0.05). Results: One-way ANOVA and Tukey post-hoc test showed that the SBS of different groups were significantly different and was impacted by different timing of bonding (P < 0.05). The main differences were between the control group (17.02 ± 6.38 MPa) and Group 1 (6.93 ± 4.3 MPa). The ARI scores showed that there were no significant differences between the four tested groups. Conclusions: The SBS of the brackets bonded 15 days after the application of the fluoride was set back to an optimal value. PMID:28197397

Design/analysis of the JWST ISIM bonded joints for survivability at cryogenic temperatures

NASA Astrophysics Data System (ADS)

Bartoszyk, Andrew; Johnston, John; Kaprielian, Charles; Kuhn, Jonathan; Kunt, Cengiz; Rodini, Benjamin; Young, Daniel

2005-08-01

A major design and analysis challenge for the JWST ISIM structure is thermal survivability of metal/composite adhesively bonded joints at the cryogenic temperature of 30K (-405°F). Current bonded joint concepts include internal invar plug fittings, external saddle titanium/invar fittings and composite gusset/clip joints all bonded to hybrid composite tubes (75mm square) made with M55J/954-6 and T300/954-6 prepregs. Analytical experience and design work done on metal/composite bonded joints at temperatures below that of liquid nitrogen are limited and important analysis tools, material properties, and failure criteria for composites at cryogenic temperatures are sparse in the literature. Increasing this challenge is the difficulty in testing for these required tools and properties at cryogenic temperatures. To gain confidence in analyzing and designing the ISIM joints, a comprehensive joint development test program has been planned and is currently running. The test program is designed to produce required analytical tools and develop a composite failure criterion for bonded joint strengths at cryogenic temperatures. Finite element analysis is used to design simple test coupons that simulate anticipated stress states in the flight joints; subsequently, the test results are used to correlate the analysis technique for the final design of the bonded joints. In this work, we present an overview of the analysis and test methodology, current results, and working joint designs based on developed techniques and properties.

Short and long term behaviour of externally bonded fibre reinforced polymer laminates with bio-based resins for flexural strengthening of concrete beams

NASA Astrophysics Data System (ADS)

McSwiggan, Ciaran

The use of bio-based resins in composites for construction is emerging as a way to reduce of embodied energy produced by a structural system. In this study, two types of bio-based resins were explored: an epoxidized pine oil resin blend (EP) and a furfuryl alcohol resin (FA) derived from corn cobs and sugar cane. Nine large-scale reinforced concrete beams strengthened using externally bonded carbon and glass fibre reinforced bio-based polymer (CFRP and GFRP) sheets were tested. The EP resin resulted in a comparable bond strength to conventional epoxy (E) when used in wet layup, with a 7% higher strength for CFRP. The FA resin, on the other hand, resulted in a very weak bond, likely due to concrete alkalinity affecting curing. However, when FA resin was used to produce prefabricated cured CFRP plates which were then bonded to concrete using conventional epoxy paste, it showed an excellent bond strength. The beams achieved an increase in peak load ranging from 18-54% and a 9-46% increase in yielding load, depending on the number of FRP layers and type of fibres and resin. Additionally, 137 concrete prisms with a mid-span half-depth saw cut were used to test CFRP bond durability, and 195 CFRP coupons were used to examine tensile strength durability. Specimens were conditioned in a 3.5% saline solution at 23, 40 or 50°C, for up to 240 days. Reductions in bond strength did not exceed 15%. Bond failure of EP was adhesive with traces of cement paste on CFRP, whereas that of FA was cohesive with a thicker layer of concrete on CFRP, suggesting that the bond between FA and epoxy paste is excellent. EP tension coupons had similar strength and modulus to E resin, whereas FA coupons had a 9% lower strength and 14% higher modulus. After 240 days of exposure, maximum reductions in tensile strength were 8, 19 and 10% for EP, FA and E resins, respectively. Analysis of Variance (ANOVA) was also performed to assess the significance of the reductions observed. High degrees of variability in the test results may have skewed the results from this statistical analysis.

The structural basis of urea-induced protein unfolding in β-catenin

PubMed Central

Wang, Chao; Chen, Zhongzhou; Hong, Xia; Ning, Fangkun; Liu, Haolin; Zang, Jianye; Yan, Xiaoxue; Kemp, Jennifer; Musselman, Catherine A.; Kutateladze, Tatinna G.; Zhao, Rui; Jiang, Chengyu; Zhang, Gongyi

2014-01-01

Although urea and guanidine hydrochloride are commonly used to denature proteins, the molecular underpinnings of this process have remained unclear for a century. To address this question, crystal structures of β-catenin were determined at various urea concentrations. These structures contained at least 105 unique positions that were occupied by urea molecules, each of which interacted with the protein primarily via hydrogen bonds. Hydrogen-bond competition experiments showed that the denaturing effects of urea were neutralized when polyethylene glycol was added to the solution. These data suggest that urea primarily causes proteins to unfold by competing and disrupting hydrogen bonds in proteins. Moreover, circular-dichroism spectra and nuclear magnetic resonance (NMR) analysis revealed that a similar mechanism caused protein denaturation in the absence of urea at pH levels greater than 12. Taken together, the results led to the conclusion that the disruption of hydrogen bonds is a general mechanism of unfolding induced by urea, high pH and potentially other denaturing agents such as guanidine hydrochloride. Traditionally, the disruption of hydrophobic inter­actions instead of hydrogen bonds has been thought to be the most important cause of protein denaturation. PMID:25372676

The structural basis of urea-induced protein unfolding in β-catenin.

PubMed

Wang, Chao; Chen, Zhongzhou; Hong, Xia; Ning, Fangkun; Liu, Haolin; Zang, Jianye; Yan, Xiaoxue; Kemp, Jennifer; Musselman, Catherine A; Kutateladze, Tatinna G; Zhao, Rui; Jiang, Chengyu; Zhang, Gongyi

2014-11-01

Although urea and guanidine hydrochloride are commonly used to denature proteins, the molecular underpinnings of this process have remained unclear for a century. To address this question, crystal structures of β-catenin were determined at various urea concentrations. These structures contained at least 105 unique positions that were occupied by urea molecules, each of which interacted with the protein primarily via hydrogen bonds. Hydrogen-bond competition experiments showed that the denaturing effects of urea were neutralized when polyethylene glycol was added to the solution. These data suggest that urea primarily causes proteins to unfold by competing and disrupting hydrogen bonds in proteins. Moreover, circular-dichroism spectra and nuclear magnetic resonance (NMR) analysis revealed that a similar mechanism caused protein denaturation in the absence of urea at pH levels greater than 12. Taken together, the results led to the conclusion that the disruption of hydrogen bonds is a general mechanism of unfolding induced by urea, high pH and potentially other denaturing agents such as guanidine hydrochloride. Traditionally, the disruption of hydrophobic interactions instead of hydrogen bonds has been thought to be the most important cause of protein denaturation.

Hydrolytic cleavage of pyroglutamyl-peptide bond. V. selective removal of pyroglutamic acid from biologically active pyroglutamylpeptides in high concentrations of aqueous methanesulfonic acid.

PubMed

Kobayashi, Junko; Ohki, Kazuhiro; Okimura, Keiko; Hashimoto, Tadashi; Sakura, Naoki

2006-06-01

Application of aqueous methanesulfonic acid (MSA) for selective chemical removal of pyroglutamic acid (pGlu) residue from five biologically active pyroglutamyl-peptides (pGlu-X-peptides, X=amino acid residue at position 2) was examined. Gonadotropin releasing hormone (Gn-RH), dog neuromedin U-8 (d-NMU-8), physalaemin (PH), a bradykinin potentiating peptide (BPP-5a) and neurotensin (NT) as pGlu-X-peptides were incubated in either 70% or 90% aqueous MSA at 25 degrees C. HPLC analysis of the incubation solutions showed that the main decomposition product was H-X-peptide derived from each pGlu-X-peptide by the removal of pGlu. The results revealed that the pGlu-X peptide bond had higher susceptibility than various internal amide bonds in the five peptides examined, including the Trp-Ser bond in Gn-RH, the C-terminal Asn-NH(2) in d-NMU-8, and the Asp-Pro bond in PH, whose acid susceptibility is well known. Thus, mild hydrolysis with high concentrations of aqueous MSA may be applicable to chemically selective removal of pGlu from pGlu-X-peptides for structural examinations.

Bond-slip detection of concrete-encased composite structure using electro-mechanical impedance technique

NASA Astrophysics Data System (ADS)

Liang, Yabin; Li, Dongsheng; Parvasi, Seyed Mohammad; Kong, Qingzhao; Lim, Ing; Song, Gangbing

2016-09-01

Concrete-encased composite structure is a type of structure that takes the advantages of both steel and concrete materials, showing improved strength, ductility, and fire resistance compared to traditional reinforced concrete structures. The interface between concrete and steel profiles governs the interaction between these two materials under loading, however, debonding damage between these two materials may lead to severe degradation of the load transferring capacity which will affect the structural performance significantly. In this paper, the electro-mechanical impedance (EMI) technique using piezoceramic transducers was experimentally investigated to detect the bond-slip occurrence of the concrete-encased composite structure. The root-mean-square deviation is used to quantify the variations of the impedance signatures due to the presence of the bond-slip damage. In order to verify the validity of the proposed method, finite element model analysis was performed to simulate the behavior of concrete-steel debonding based on a 3D finite element concrete-steel bond model. The computed impedance signatures from the numerical results are compared with the results obtained from the experimental study, and both the numerical and experimental studies verify the proposed EMI method to detect bond slip of a concrete-encased composite structure.

Parental bonding in males with adjustment disorder and hyperventilation syndrome.

PubMed

Lung, For-Wey; Lee, Ting-Hsuan; Huang, Mei-Feng

2012-06-06

The purpose of the study was to identify the style of parental bonding and the personality characteristics that might increase the risk of hyperventilation and adjustment disorder. A total of 917 males were recruited, 156 with adjustment disorder and hyperventilation syndrome (AD + HY), 273 with adjustment disorder without hyperventilation syndrome (AD-HY), and 488 healthy controls. All participants completed the Parental Bonding Instrument, Eysenck Personality Questionnaire, and Chinese Health Questionnaire. Analysis using structural equation models identified a pathway relationship in which parental bonding affected personality characteristics, personality characteristics affected mental health condition, and mental health condition affected the development of hyperventilation or adjustment disorder. Males with AD-HY perceived less paternal care, and those with AD + HY perceived more maternal protection than those with adjustment disorder and those in the control group. Participants with AD-HY were more neurotic and less extroverted than those with AD + HY. Both groups showed poorer mental health than the controls. Although some patients with hyperventilation syndrome demonstrated symptoms of adjustment disorder, there were different predisposing factors between the two groups in terms of parental bonding and personality characteristics. This finding is important for the early intervention and prevention of hyperventilation and adjustment disorder.

[Compatibility between high-strength dental ceramic (type A) and vintage AL veneering porcelain].

PubMed

Cui, Jun; Chao, Yong-lie; Meng, Yu-kun

2006-05-01

To investigate the interface bond strength and compatibility between High-Strength Dental Ceramic (type A) and Vintage AL veneering porcelain. Twenty bar-shape specimens (ten Vintage AL and ten Vitadur alpha) were fabricated, and shear test was conducted to determine the bond strength. A bilayered composite (1 mm core ceramic and 0.8 mm Vintage AL) was prepared and then fractured for scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis. Ten all-ceramic anterior crowns were fabricated and the temperatures of thermal shock resistance were tested. The mean values of the bond strength measured were (55.52 +/- 14.64) MPa and (59.37 +/- 13.93) MPa for Vintage AL and Vitadur alpha respectively (P>0.05). SEM showed tight connection between the High-Strength Dental Ceramic (type A) and the veneering porcelain. Element diffusion was also confirmed by energy dispersive spectroscopy (EDS) analysis. The temperature of thermal shock resistance of this system was (179 +/- 15) degrees C. Vintage AL veneering porcelain has good thermal and chemical compatibility with High-Strength Dental Ceramic (type A).

Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo

2015-12-21

Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53–75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol atmore » a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.« less

Monitoring the informational efficiency of European corporate bond markets with dynamical permutation min-entropy

NASA Astrophysics Data System (ADS)

Zunino, Luciano; Bariviera, Aurelio F.; Guercio, M. Belén; Martinez, Lisana B.; Rosso, Osvaldo A.

2016-08-01

In this paper the permutation min-entropy has been implemented to unveil the presence of temporal structures in the daily values of European corporate bond indices from April 2001 to August 2015. More precisely, the informational efficiency evolution of the prices of fifteen sectorial indices has been carefully studied by estimating this information-theory-derived symbolic tool over a sliding time window. Such a dynamical analysis makes possible to obtain relevant conclusions about the effect that the 2008 credit crisis has had on the different European corporate bond sectors. It is found that the informational efficiency of some sectors, namely banks, financial services, insurance, and basic resources, has been strongly reduced due to the financial crisis whereas another set of sectors, integrated by chemicals, automobiles, media, energy, construction, industrial goods & services, technology, and telecommunications has only suffered a transitory loss of efficiency. Last but not least, the food & beverage, healthcare, and utilities sectors show a behavior close to a random walk practically along all the period of analysis, confirming a remarkable immunity against the 2008 financial crisis.

Structural and Antioxidant Properties of Compounds Obtained from Fe2+ Chelation by Juglone and Two of Its Derivatives: DFT, QTAIM, and NBO Studies

PubMed Central

Tamafo Fouegue, Aymard Didier; Bikélé Mama, Désiré; Nkungli, Nyiang Kennet; Younang, Elie

2016-01-01

The chelating ability of juglone and two of its derivatives towards Fe2+ion and the antioxidant activity (AOA) of the resulting chelates and complexes (in the presence of H2O and CH3OH as ligands) in gas phase is reported via bond dissociation enthalpy, ionization potential, proton dissociation enthalpy, proton affinity, and electron transfer enthalpy. The DFT/B3LYP level of theory associated with the 6-31+G(d,p) and 6-31G(d) Pople-style basis sets on the atoms of the ligands and the central Fe(II), respectively, was used. Negative chelation free energies obtained revealed that juglone derivatives possessing the O-H substituent (L2) have the greatest ability to chelate Fe2+ ion. Apart from 1B, thermodynamic descriptors of the AOA showed that the direct hydrogen atom transfer is the preferred mechanism of the studied molecules. NBO analysis showed that the Fe-ligand bonds are all formed through metal to ligand charge transfer. QTAIM studies revealed that among all the Fe-ligand bonds, the O1-Fe bond of 1A is purely covalent. The aforementioned results show that the ligands can be used to fight against Fe(II) toxicity, thus preserving human health, and fight against the deterioration of industrial products. In addition, most of the complexes studied have shown a better AOA than their corresponding ligands. PMID:27774044

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations.

PubMed

Chen, Ying; Bylaska, Eric J; Weare, John H

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick). The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe 3+ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe 3+ . The water molecules capping surface Fe 3+ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe 3+ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe 3+ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe 3+ , those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe 3+ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism. Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe-OH 2 distances in the DFT calculations it was proposed that the surface Fe 3+ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination. Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe 3+ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe 3+ is coordinated with only 5 neighbors.

Resin composite repair: Quantitative microleakage evaluation of resin-resin and resin-tooth interfaces with different surface treatments

PubMed Central

Celik, Cigdem; Cehreli, Sevi Burcak; Arhun, Neslihan

2015-01-01

Objective: The aim was to evaluate the effect of different adhesive systems and surface treatments on the integrity of resin-resin and resin-tooth interfaces after partial removal of preexisting resin composites using quantitative image analysis for microleakage testing protocol. Materials and Methods: A total of 80 human molar teeth were restored with either of the resin composites (Filtek Z250/GrandioSO) occlusally. The teeth were thermocycled (1000×). Mesial and distal 1/3 parts of the restorations were removed out leaving only middle part. One side of the cavity was finished with course diamond bur and the other was air-abraded with 50 μm Al2O3. They were randomly divided into four groups (n = 10) to receive: Group 1: Adper Single Bond 2; Group 2: All Bond 3; Group 3: ClearfilSE; Group 4: BeautiBond, before being repaired with the same resin composite (Filtek Z250). The specimens were re-thermocycled (1000×), sealed with nail varnish, stained with 0.5% basic fuchsin, sectioned mesiodistally and photographed digitally. The extent of dye penetration was measured by image analysis software (ImageJ) for both bur-finished and air-abraded surfaces at resin-tooth and resin-resin interfaces. The data were analyzed statistically. Results: BeautiBond exhibited the most microleakage at every site. Irrespective of adhesive and initial composite type, air-abrasion showed less microleakage except for BeautiBond. The type of initial repaired restorative material did not affect the microleakage. BeautiBond adhesive may not be preferred in resin composite repair in terms of microleakage prevention. Conclusions: Surface treatment with air-abrasion produced the lowest microleakage scores, independent of the adhesive systems and the pre-existing resin composite type. Pre-existing composite type does not affect the microleakage issue. All-in-one adhesive resin (BeautiBond) may not be preferred in resin composite repair in terms of microleakage prevention. PMID:25713491

Specific energy contributions from competing hydrogen-bonded structures in six polymorphs of phenobarbital.

PubMed

Gelbrich, Thomas; Braun, Doris E; Griesser, Ulrich J

2016-01-01

In solid state structures of organic molecules, identical sets of H-bond donor and acceptor functions can result in a range of distinct H-bond connectivity modes. Specifically, competing H-bond structures (HBSs) may differ in the quantitative proportion between one-point and multiple-point H-bond connections. For an assessment of such HBSs, the effects of their internal as well as external (packing) interactions need to be taken into consideration. The semi-classical density sums (SCDS-PIXEL) method, which enables the calculation of interaction energies for molecule-molecule pairs, was used to investigate six polymorphs of phenobarbital (Pbtl) with different quantitative proportions of one-point and two-point H-bond connections. The structures of polymorphs V and VI of Pbtl were determined from single crystal data. Two-point H-bond connections are inherently inflexible in their geometry and lie within a small PIXEL energy range (-45.7 to -49.7 kJ mol(-1)). One-point H-bond connections are geometrically less restricted and subsequently show large variations in their dispersion terms and total energies (-23.1 to -40.5 kJ mol(-1)). The comparison of sums of interaction energies in small clusters containing only the strongest intermolecular interactions showed an advantage for compact HBSs with multiple-point connections, whereas alternative HBSs based on one-point connections may enable more favourable overall packing interactions (i.e. V vs. III). Energy penalties associated with experimental intramolecular geometries relative to the global conformational energy minimum were calculated and used to correct total PIXEL energies. The estimated order of stabilities (based on PIXEL energies) is III > I > II > VI > X > V, with a difference of just 1.7 kJ mol(-1) between the three most stable forms. For an analysis of competing HBSs, one has to consider the contributions from internal H-bond and non-H-bond interactions, from the packing of multiple HBS instances and intramolecular energy penalties. A compact HBS based on multiple-point H-bond connections should typically lead to more packing alternatives and ultimately to a larger number of viable low-energy structures than a competing one-point HBS (i.e. dimer vs. catemer). Coulombic interaction energies associated with typical short intermolecular C-H···O contact geometries are small in comparison with dispersion effects associated with the packing complementary molecular shapes.Graphical abstractCompeting H-bond motifs can differ markedly in their energy contributions.

Contamination and Surface Preparation Effects on Composite Bonding

NASA Technical Reports Server (NTRS)

Kutscha, Eileen O.; Vahey, Paul G.; Belcher, Marcus A.; VanVoast, Peter J.; Grace, William B.; Blohowiak, Kay Y.; Palmieri, Frank L.; Connell, John W.

2017-01-01

Results presented here demonstrate the effect of several prebond surface contaminants (hydrocarbon, machining fluid, latex, silicone, peel ply residue, release film) on bond quality, as measured by fracture toughness and failure modes of carbon fiber reinforced epoxy substrates bonded in secondary and co-bond configurations with paste and film adhesives. Additionally, the capability of various prebond surface property measurement tools to detect contaminants and potentially predict subsequent bond performance of three different adhesives is also shown. Surface measurement methods included water contact angle, Dyne solution wettability, optically stimulated electron emission spectroscopy, surface free energy, inverse gas chromatography, and Fourier transform infrared spectroscopy with chemometrics analysis. Information will also be provided on the effectiveness of mechanical and energetic surface treatments to recover a bondable surface after contamination. The benefits and drawbacks of the various surface analysis tools to detect contaminants and evaluate prebond surfaces after surface treatment were assessed as well as their ability to correlate to bond performance. Surface analysis tools were also evaluated for their potential use as in-line quality control of adhesive bonding parameters in the manufacturing environment.

TEM Analysis of Interfaces in Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

NASA Technical Reports Server (NTRS)

Ozaki, T.; Tsuda, H.; Halbig, M. C.; Singh, M.; Hasegawa, Y.; Mori, S.; Asthana R.

2016-01-01

Silicon Carbide (SiC) is a promising material for thermo-structural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, and Mo-B. In this presentation, the result of microstructural analysis obtained by TEM observations and the influence of metallic interlayers and fiber orientation of SA-THX on the joint microstructure will be discussed.

Influence of preheating the bonding agent of a conventional three-step adhesive system and the light activated resin cement on dentin bond strength

PubMed Central

Holanda, Daniel Brandão Vilela; França, Fabiana Mantovani Gomes; do Amaral, Flávia Lucisano Botelho; Flório, Flávia Martão; Basting, Roberta Tarkany

2013-01-01

Aims: to evaluate the influence of preheating the bonding agent (Scotchbond Multipurpose Adhesive/3M ESPE) and the light-activated resin cement (RelyX Venner/3M ESPE) on dentin microtensile bond strength. Materials and Methods: The exposed flat dentin surface of 40 human third molars were randomly distributed into four groups for cementation (SR Adoro/Ivoclar Vivadent) (n = 10): G1-bond and resin cement, both at room temperature (22°C), G2-bond preheated to 58°C and cement at room temperature (22°C), G3-bond at room temperature (22°C) and the cement preheated to 58°C, G4-bond preheated to 58°C and cement preheated to 58°C. Sticks of dentin/block set measuring approximately 1 mm2 were obtained and used for the microtensile bond strength test. All sticks had their failure mode classified. Statistical analysis used: Factorial analysis of variance was applied, 2 × 2 (bond × cement) (P < 0.05). Results: Preheating the bonding agent (P = 0.8411) or the cement (P = 0.7155), yielded no significant difference. The interaction bond × cement was not significant (P = 0.9389). Conclusions: Preheating the bond and/or the light-activated resin cement did not influence dentin bond strength or fracture failure mode. PMID:24347889

Shear Bond Strength of Orthodontic Brackets Bonded to Zirconium Crowns

PubMed Central

Mehmeti, Blerim; Azizi, Bleron; Kelmendi, Jeta; Iljazi-Shahiqi, Donika; Alar, Željko

2017-01-01

Background An increasing demand for esthetic restorations has resulted in an increased use of all-ceramic restorations, such as zirconium. However, one of the challenges the orthodontist must be willing to face is how to increase bond strength between the brackets and various ceramic restorations.Bond strength can beaffected bybracket type, by the material that bracketsaremade of, and their base surface design or retention mode. ​ Aim: of this study was to perform a comparative analysis of the shear bond strength (SBS) of metallic and ceramic orthodontic brackets bonded to all-zirconium ceramic surfaces used for prosthetic restorations, and also to evaluate the fracture mode of these two types of orthodontic brackets. Material and methods Twenty samples/semi-crowns of all-zirconium ceramic, on which orthodontic brackets were bonded, 10 metallic and 10 ceramic polycrystalline brackets, were prepared for this research. SBS has been testedby Universal Testing Machine, with a load applied using a knife edged rod moving at a fixed rate of 1 mm/min, until failure occurred. The force required to debond the brackets was recorded in Newton, then SBS was calculated to MPa. In addition, the samples were analyzed using a digital camera magnifier to determine Adhesive Remnant Index (ARI). Statistical data were processed using t-test, and the level of significance was set at α = 0.05. Results Higher shear bond strength values were observed in metallic brackets bonded to zirconium crowns compared tothoseof ceramic brackets, with a significant difference. During the test, two of the ceramic brackets were partially or totally damaged. Conclusion Metallic brackets, compared to ceramic polycrystalline brackets, seemed tocreate stronger adhesion with all-zirconium surfaces due to their better retention mode. Also, ceramic brackets showed higher fragility during debonding. PMID:28827846

Shear Bond Strength of Orthodontic Brackets Bonded to Zirconium Crowns.

PubMed

Mehmeti, Blerim; Azizi, Bleron; Kelmendi, Jeta; Iljazi-Shahiqi, Donika; Alar, Željko; Anić-Milošević, Sandra

2017-06-01

An increasing demand for esthetic restorations has resulted in an increased use of all-ceramic restorations, such as zirconium. However, one of the challenges the orthodontist must be willing to face is how to increase bond strength between the brackets and various ceramic restorations.Bond strength can beaffected bybracket type, by the material that bracketsaremade of, and their base surface design or retention mode. ​: A im: of this study was to perform a comparative analysis of the shear bond strength (SBS) of metallic and ceramic orthodontic brackets bonded to all-zirconium ceramic surfaces used for prosthetic restorations, and also to evaluate the fracture mode of these two types of orthodontic brackets. Twenty samples/semi-crowns of all-zirconium ceramic, on which orthodontic brackets were bonded, 10 metallic and 10 ceramic polycrystalline brackets, were prepared for this research. SBS has been testedby Universal Testing Machine, with a load applied using a knife edged rod moving at a fixed rate of 1 mm/min, until failure occurred. The force required to debond the brackets was recorded in Newton, then SBS was calculated to MPa. In addition, the samples were analyzed using a digital camera magnifier to determine Adhesive Remnant Index (ARI). Statistical data were processed using t-test, and the level of significance was set at α = 0.05. Higher shear bond strength values were observed in metallic brackets bonded to zirconium crowns compared tothoseof ceramic brackets, with a significant difference. During the test, two of the ceramic brackets were partially or totally damaged. Metallic brackets, compared to ceramic polycrystalline brackets, seemed tocreate stronger adhesion with all-zirconium surfaces due to their better retention mode. Also, ceramic brackets showed higher fragility during debonding.

Effect of acid and laser etching on shear bond strength of conventional and resin-modified glass-ionomer cements to composite resin.

PubMed

Navimipour, Elmira Jafari; Oskoee, Siavash Savadi; Oskoee, Parnian Alizadeh; Bahari, Mahmoud; Rikhtegaran, Sahand; Ghojazadeh, Morteza

2012-03-01

Success in sandwich technique procedures can be achieved through an acceptable bond between the materials. The aim of this study was to compare the effect of 35% phosphoric acid and Er,Cr:YSGG laser on shear bond strength of conventional glass-ionomer cement (GIC) and resin-modified glass-ionomer cement (RMGIC) to composite resin in sandwich technique. Sixty-six specimens were prepared from each type of glass-ionomer cements and divided into three treatment groups as follows: without pretreatment, acid etching by 35% phosphoric acid for 15 s, and 1-W Er,Cr:YSGG laser treatment for 15 s with a 600-μm-diameter tip aligned perpendicular to the target area at a distance of 1 mm from the surface. Energy density of laser irradiation was 17.7 J/cm(2). Two specimens in each group were prepared for evaluation under a scanning electron microscope (SEM) after surface treatment and the remainder underwent bonding procedure with a bonding agent and composite resin. Then the shear bond strength was measured at a crosshead speed of 0.5 mm/min. Two-factor analysis of variance and post-hoc Tukey test showed that the cement type, surface treatment method, and the interaction of these two factors significantly affect the shear bond strength between glass-ionomer cements and composite resin (p < 0.05). Surface treatment with phosphoric acid or Er,Cr:YSGG laser increased the shear bond strength of GIC to composite resin; however, in RMGIC only laser etching resulted in significantly higher bond strength. These findings were supported by SEM results. The fracture mode was evaluated under a stereomicroscope at ×20.

Effect of Bioactive Glass air Abrasion on Shear Bond Strength of Two Adhesive Resins to Decalcified Enamel

PubMed Central

Eshghi, Alireza; Khoroushi, Maryam; Rezvani, Alireza

2014-01-01

Objective: Bioactive glass air abrasion is a conservative technique to remove initial decalcified tissue and caries. This study examined the shear bond strength of composite resin to sound and decalcified enamel air-abraded by bioactive glass (BAG) or alumina using etch-and-rinse and self-etch adhesives. Materials and Methods: Forty-eight permanent molars were root-amputated and sectioned mesiodistally. The obtained 96 specimens were mounted in acrylic resin; the buccal and lingual surfaces remained exposed. A demineralizing solution was used to decalcify half the specimens. Both sound and decalcified specimens were divided into two groups of alumina and bioactive glass air abrasion. In each group, the specimens were subdivided into two subgroups of Clearfil SE Bond or OptiBond FL adhesives (n=12). Composite resin cylinders were bonded on enamel surfaces cured and underwent thermocycling. The specimens were tested for shear bond strength. Data were analyzed using SPSS 16.0 and three-way ANOVA (α=0.05). Similar to the experimental groups, the enamel surface of one specimen underwent SEM evaluation. Results: No significant differences were observed in composite resin bond strength subsequent to alumina or bioactive glass air abrasion preparation techniques (P=0.987). There were no statistically significant differences between the bond strength of etch-and-rinse and self-etch adhesive groups (P=1). Also, decalcified or intact enamel groups had no significant difference (P=0.918). However, SEM analysis showed much less enamel irregularities with BAG air abrasion compared to alumina air abrasion. Conclusion: Under the limitations of this study, preparation of both intact and decalcified enamel surfaces with bioactive glass air abrasion results in similar bond strength of composite resin in comparison with alumina air abrasion using etch-&-rinse or self-etch adhesives. PMID:25628694

Banding versus bonding of first permanent molars: a multi-centre randomized controlled trial.

PubMed

Nazir, Mariyah; Walsh, Tanya; Mandall, Nicky A; Matthew, Susie; Fox, Dee

2011-06-01

To assess the effectiveness of banding versus bonding of first permanent molars during fixed appliance treatment; in terms of attachment failure, patient discomfort and post-treatment enamel demineralization. Multi-centre randomized clinical trial. One District General Hospital Orthodontic Department and two Specialist Orthodontic Practices. Orthodontic patients aged between 10 and 18 years old, randomly allocated to either receive molar bands (n=40) or molar bonds (n=40). Bands were cemented with a conventional glass ionomer cement and tubes were bonded with light-cured composite to all four first permanent molar teeth for each subject. Attachments were reviewed at each recall appointment to assess loosening or loss. The clinical end point of the trial was the day of appliance debond. Enamel demineralization at debond was assessed using the modified International Caries Assessment and Detection System (ICDAS). The first time failure rate for molar bonds was 18·4% and 2·6% for molar bands (P=0·0002). Survival analysis demonstrated molar bonds were more likely to fail compared with molar bands. First permanent molars with bonded tubes experienced more demineralization than those with cemented bands (P=0·027). There was no statistically significant difference in discomfort experienced by patients after banding or bonding first permanent molars (P>0·05). This study shows that as part of fixed appliance therapy, American Orthodontics photoetched first permanent molar bands cemented with 3M ESPE Ketac-Cem perform better than American Orthodontics low profile photo-etched and mesh-based first permanent molar tubes bonded with 3M Unitek Transbond XT in terms of failure behaviour and molar enamel demineralization.

Quantitative Percussion Diagnostics For Evaluating Bond Integrity Between Composite Laminates

NASA Astrophysics Data System (ADS)

Poveromo, Scott Leonard

Conventional nondestructive testing (NDT) techniques used to detect defects in composites are not able to determine intact bond integrity within a composite structure and are costly to use on large and complex shaped surfaces. To overcome current NDT limitations, a new technology was utilized based on quantitative percussion diagnostics (QPD) to better quantify bond quality in fiber reinforced composite materials. Experimental results indicate that this technology is capable of detecting 'kiss' bonds (very low adhesive shear strength), caused by the application of release agents on the bonding surfaces, between flat composite laminates bonded together with epoxy adhesive. Specifically, the local value of the loss coefficient determined from quantitative percussion testing was found to be significantly greater for a release coated panel compared to that for a well bonded sample. Also, the local value of the probe force or force returned to the probe after impact was observed to be lower for the release coated panels. The increase in loss coefficient and decrease in probe force are thought to be due to greater internal friction during the percussion event for poorly bonded specimens. NDT standards were also fabricated by varying the cure parameters of an epoxy film adhesive. Results from QPD for the variable cure NDT standards and lap shear strength measurements taken of mechanical test specimens were compared and analyzed. Finally, experimental results have been compared to a finite element analysis to understand the visco-elastic behavior of the laminates during percussion testing. This comparison shows how a lower quality bond leads to a reduction in the percussion force by biasing strain in the percussion tested side of the panel.

Ab-initio study of structural, electronic, and transport properties of zigzag GaP nanotubes.

PubMed

Srivastava, Anurag; Jain, Sumit Kumar; Khare, Purnima Swarup

2014-03-01

Stability and electronic properties of zigzag (3 ≤ n ≤ 16) gallium phosphide nanotubes (GaP NTs) have been analyzed by employing a systematic ab-intio approach based on density functional theory using generalized gradient approximation with revised Perdew Burke Ernzerhoff type parameterization. Diameter dependence of bond length, buckling, binding energy, and band gap has been investigated and the analysis shows that the bond length and buckling decreases with increasing diameter of the tube, highest binding energy of (16, 0) confirms this as the most stable amongst all the NTs taken into consideration. The present GaP NTs shows direct band gap and it increases with diameter of the tubes. Using a two probe model for (4, 0) NT the I-V relationship shows an exponential increase in current on applying bias voltage beyond 1.73 volt.

Capping Ligand Vortices as “Atomic Orbitals” in Nanocrystal Self-Assembly

DOE PAGES

Waltmann, Curt; Horst, Nathan; Travesset, Alex

2017-10-27

In this work, we present a detailed analysis of the interaction between two nanocrystals capped with ligands consisting of hydrocarbon chains by united atom molecular dynamics simulations. We show that the bonding of two nanocrystals is characterized by ligand textures in the form of vortices. These results are generalized to nanocrystals of different types (differing core and ligand sizes) where the structure of the vortices depends on the softness asymmetry. We provide rigorous calculations for the binding free energy, show that these energies are independent of the chemical composition of the cores, and derive analytical formulas for the equilibrium separation.more » We discuss the implications of our results for the self-assembly of single-component and binary nanoparticle superlattices. Overall, our results show that the structure of the ligands completely determines the bonding of nanocrystals, fully supporting the predictions of the recently proposed Orbifold topological model.« less

Capping Ligand Vortices as "Atomic Orbitals" in Nanocrystal Self-Assembly.

PubMed

Waltmann, Curt; Horst, Nathan; Travesset, Alex

2017-11-28

We present a detailed analysis of the interaction between two nanocrystals capped with ligands consisting of hydrocarbon chains by united atom molecular dynamics simulations. We show that the bonding of two nanocrystals is characterized by ligand textures in the form of vortices. These results are generalized to nanocrystals of different types (differing core and ligand sizes) where the structure of the vortices depends on the softness asymmetry. We provide rigorous calculations for the binding free energy, show that these energies are independent of the chemical composition of the cores, and derive analytical formulas for the equilibrium separation. We discuss the implications of our results for the self-assembly of single-component and binary nanoparticle superlattices. Overall, our results show that the structure of the ligands completely determines the bonding of nanocrystals, fully supporting the predictions of the recently proposed Orbifold topological model.

Influence of different adhesive systems on the pull-out bond strength of glass fiber posts.

PubMed

da Silva, Luciana Mendonça; Andrade, Andréa Mello de; Machuca, Melissa Fernanda Garcia; da Silva, Paulo Maurício Batista; da Silva, Ricardo Virgolino C; Veronezi, Maria Cecília

2008-01-01

This in vitro study evaluated the tensile bond strength of glass fiber posts (Reforpost - Angelus-Brazil) cemented to root dentin with a resin cement (RelyX ARC - 3M/ESPE) associated with two different adhesive systems (Adper Single Bond - 3M/ESPE and Adper Scotchbond Multi Purpose (MP) Plus - 3M/ESPE), using the pull-out test. Twenty single-rooted human teeth with standardized root canals were randomly assigned to 2 groups (n=10): G1- etching with 37% phosphoric acid gel (3M/ESPE) + Adper Single Bond + #1 post (Reforpost - Angelus) + four #1 accessory posts (Reforpin - Angelus) + resin cement; G2- etching with 37% phosphoric acid gel + Adper Scotchbond MP Plus + #1 post + four #1 accessory posts + resin cement. The specimens were stored in distilled water at 37 degrees C for 7 days and submitted to the pull-out test in a universal testing machine (EMIC) at a crosshead speed of 0.5 mm/min. The mean values of bond strength (kgf) and standard deviation were: G1- 29.163 +/- 7.123; G2- 37.752 +/-13.054. Statistical analysis (Student's t-test; a=0.05 showed no statistically significant difference (p<0.05) between the groups. Adhesive bonding failures between resin cement and root canal dentin surface were observed in both groups, with non-polymerized resin cement in the apical portion of the post space when Single Bond was used (G1). The type of adhesive system employed on the fiber post cementation did not influence the pull-out bond strength.

A comparison between the shear bond strength of brackets bonded to glazed and deglazed porcelain surfaces with resin-reinforced glass-ionomer cement and a bis-GMA resin adhesive.

PubMed

Lifshitz, Abraham B; Cárdenas, Marianela

2006-01-01

This study compared the shear bond strength of a light-cure resin-reinforced glass-ionomer cement with a bis-GMA light-cure resin system in the bonding of stainless steel brackets to glazed and deglazed porcelain surfaces. Porcelain surfaces were divided into 4 groups: group 1, deglazed porcelain surfaces with Transbond XT, group 2, glazed porcelain surfaces with Transbond XT; group 3, deglazed porcelain surfaces with Fuji Ortho LC; and group 4, porcelain surfaces with Fuji Ortho LC. Microetching with 50-microm aluminum oxide for 2 seconds at a distance of 5 mm deglazed the porcelain surfaces in groups 1 and 3. All brackets were bonded to the porcelain surfaces using the same procedure and light-cured for 40 seconds with a visible light. All samples were thermocycled between 5 degrees C and 55 degrees C for 300 cycles before testing for shear bond strength with a universal testing machine. The analysis of variance showed no significant difference (P < .05) among the 4 groups; ie, group 1, 10.12 MPa; group 2, 7.00 MPa; group 3, 6.78 MPa; and group 4, 11.15 MPa. The F test also failed to demonstrate any statistical difference among the groups. Conditioning the porcelain surfaces with 37% phosphoric acid immediately followed by a nonhydrolyzed silane coupling agent resulted in clinically adequate bond strength when using either a composite resin or a resin-reinforced glass-ionomer cement. Microetching of these porcelain surfaces apparently offers no bonding advantage.

Hydrogen bonding motifs, spectral characterization, theoretical computations and anticancer studies on chloride salt of 6-mercaptopurine: An assembly of corrugated lamina shows enhanced solubility

NASA Astrophysics Data System (ADS)

Suresh Kumar, S.; Athimoolam, S.; Sridhar, B.

2015-10-01

6-Mercaptopurine (an anti cancer drug), is coming under the class II Biopharmaceutics Classification System (BCS). In order to enhance the solubility with retained physiochemical/pharmaceutical properties, the present work was attempted with its salt form. The single crystals of 6-mercaptopurinium chloride (6MPCl) were successfully grown by slow evaporation technique under ambient temperature. The X-ray diffraction study shows that the crystal packing is dominated by N-H⋯Cl classical hydrogen bonds leading to corrugated laminar network. The hydrogen bonds present in the lamina can be dismantled as three chain C21(6), C21(7) and C21(8) motifs running along ab-diagonal of the unit cell. These primary chain motifs are interlinked to each other forming ring R63(21) motifs. These chain and ring motifs are aggregated like a dendrimer structure leading to the above said corrugated lamina. This low dimensional molecular architecture differs from the ladder like arrays in pure drug though it possess lattice water molecule in lieu of the chloride anion in the present compound. Geometrical optimizations of 6MPCl were done by Density Functional Theory (DFT) using B3LYP function with two different basis sets. The optimized molecular geometries and computed vibrational spectra are compared with their experimental counterparts. The Natural Bond Orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and Intramolecular Charge Transfer (ICT). The chemical hardness, electronegativity, chemical potential and electrophilicity index of 6MPCl were found along with the HOMO-LUMO plot. The lower band gap value obtained from the Frontier Molecular Orbital (FMO) analysis reiterates the pharmaceutical activity of the compound. The anticancer studies show that 6MPCl retains its activity against human cervical cancer cell line (HeLa). Hence, this anticancer efficacy and improved solubility demands 6MPCl towards the further pharmaceutical applications.

Push-out tests on a new silicon carbide/reaction-bonded silicon carbide ceramic matrix composite

NASA Technical Reports Server (NTRS)

Curtin, William A.; Eldridge, Jeffrey I.; Srinivasan, Gajawalli V.

1993-01-01

Fiber push-out tests have been performed on a ceramic matrix composite consisting of carborundum-sintered SiC fibers, with a BN coating, embedded in a reaction-bonded SiC matrix. Analysis of the push-out data, utilizing the most complete theory presently available, shows that one of the fiber/coating/matrix interfaces has a low fracture energy (one-tenth that of the fiber) and a moderate sliding resistance of about 8 MPa. The debonded sliding interface shows some continuous but minor abrasion, which appears to increase the sliding resistance, but overall the system exhibits very clean smooth sliding. The tensile response of a full-scale composite is then modeled using data obtained here and known fiber strengths to demonstrate the good composite behavior predicted for this material.

Evaluation Of The Shear Bond Strength Between Dentin And Dental Luting Cement Following Dentin Surface Treatment By 980 Nm Diode Laser And Desensitizing Agent

NASA Astrophysics Data System (ADS)

Ibrahim, T.; Gheith, M.

2011-09-01

Dentin hypersensitivity is described clinically as an exaggerated response to non-noxious sensory stimuli. Current treatment is concentrating on two approaches; to occlude the dentinal tubules or to block neural transmission. This is achieved through using dentin desensitizers and low power lasers. Forty eight freshly extracted human molar teeth were used in this study and divided equally into three groups. Group 1) control group, group 2) laser treated dentin surface group, and group 3) desensitizing agent dentin surface group. Scanning electron microscopic analysis of laser treated group showed melted globules, no carbonization, recrystalization and crystal growth of the apatite in some areas. In diode laser dentin surface treated group showed the highest shear bond strength mean value.

Synthesis and binding affinity analysis of α1-2- and α1-6-O/S-linked dimannosides for the elucidation of sulfur in glycosidic bonds using quartz crystal microbalance sensors.

PubMed

Norberg, Oscar; Wu, Bin; Thota, Niranjan; Ge, Jian-Tao; Fauquet, Germain; Saur, Ann-Kathrin; Aastrup, Teodor; Dong, Hai; Yan, Mingdi; Ramström, Olof

2017-11-27

The role of sulfur in glycosidic bonds has been evaluated using quartz crystal microbalance methodology. Synthetic routes towards α1-2- and α1-6-linked dimannosides with S- or O-glycosidic bonds have been developed, and the recognition properties assessed in competition binding assays with the cognate lectin concanavalin A. Mannose-presenting QCM sensors were produced using photoinitiated, nitrene-mediated immobilization methods, and the subsequent binding study was performed in an automated flow-through instrumentation, and correlated with data from isothermal titration calorimetry. The recorded K d -values corresponded well with reported binding affinities for the O-linked dimannosides with affinities for the α1-2-linked dimannosides in the lower micromolar range. The S-linked analogs showed slightly disparate effects, where the α1-6-linked analog showed weaker affinity than the O-linked dimannoside, as well as positive apparent cooperativity, whereas the α1-2-analog displayed very similar binding compared to the O-linked structure. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catechol-Functionalized Synthetic Polymer as a Dental Adhesive to Contaminated Dentin Surface for a Composite Restoration.

PubMed

Lee, Sang-Bae; González-Cabezas, Carlos; Kim, Kwang-Mahn; Kim, Kyoung-Nam; Kuroda, Kenichi

2015-08-10

This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe(3+) additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe-catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives.

Catechol-Functionalized Synthetic Polymer as a Dental Adhesive to Contaminated Dentin Surface for a Composite Restoration

PubMed Central

2015-01-01

This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe3+ additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe–catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives. PMID:26176305

Protein-protein interfaces are vdW dominant with selective H-bonds and (or) electrostatics towards broad functional specificity.

PubMed

Nilofer, Christina; Sukhwal, Anshul; Mohanapriya, Arumugam; Kangueane, Pandjassarame

2017-01-01

Several catalysis, cellular regulation, immune function, cell wall assembly, transport, signaling and inhibition occur through Protein- Protein Interactions (PPI). This is possible with the formation of specific yet stable protein-protein interfaces. Therefore, it is of interest to understand its molecular principles using structural data in relation to known function. Several interface features have been documented using known X-ray structures of protein complexes since 1975. This has improved our understanding of the interface using structural features such as interface area, binding energy, hydrophobicity, relative hydrophobicity, salt bridges and hydrogen bonds. The strength of binding between two proteins is dependent on interface size (number of residues at the interface) and thus its corresponding interface area. It is known that large interfaces have high binding energy (sum of (van der Waals) vdW, H-bonds, electrostatics). However, the selective role played by each of these energy components and more especially that of vdW is not explicitly known. Therefore, it is important to document their individual role in known protein-protein structural complexes. It is of interest to relate interface size with vdW, H-bonds and electrostatic interactions at the interfaces of protein structural complexes with known function using statistical and multiple linear regression analysis methods to identify the prominent force. We used the manually curated non-redundant dataset of 278 hetero-dimeric protein structural complexes grouped using known functions by Sowmya et al. (2015) to gain additional insight to this phenomenon using a robust inter-atomic non-covalent interaction analyzing tool PPCheck (Anshul and Sowdhamini, 2015). This dataset consists of obligatory (enzymes, regulator, biological assembly), immune and nonobligatory (enzyme and regulator inhibitors) complexes. Results show that the total binding energy is more for large interfaces. However, this is not true for its individual energy factors. Analysis shows that vdW energies contribute to about 75% ± 11% on average among all complexes and it also increases with interface size (r2 ranging from 0.67 to 0.89 with p<0.01) at 95% confidence limit irrespective of molecular function. Thus, vdW is both dominant and proportional at the interface independent of molecular function. Nevertheless, H bond energy contributes to 15% ± 6.5% on average in these complexes. It also moderately increases with interface size (r2 ranging from 0.43 to 0.61 with p<0.01) only among obligatory and immune complexes. Moreover, there is about 11.3% ± 8.7% contribution by electrostatic energy. It increases with interface size specifically among non-obligatory regulator-inhibitors (r2 = 0.44). It is implied that both H-bonds and electrostatics are neither dominant nor proportional at the interface. Nonetheless, their presence cannot be ignored in binding. Therefore, H-bonds and (or) electrostatic energy having specific role for improved stability in complexes is implied. Thus, vdW is common at the interface stabilized further with selective H-bonds and (or) electrostatic interactions at an atomic level in almost all complexes. Comparison of this observation with residue level analysis of the interface is compelling. The role by H-bonds (14.83% ± 6.5% and r2 = 0.61 with p<0.01) among obligatory and electrostatic energy (8.8% ± 4.77% and r2 = 0.63 with p <0.01) among non-obligatory complexes within interfaces (class A) having more non-polar residues than surface is influencing our inference. However, interfaces (class B) having less non-polar residues than surface show 1.5 fold more electrostatic energy on average. The interpretation of the interface using inter-atomic (vdW, H-bonds, electrostatic) interactions combined with inter-residue predominance (class A and class B) in relation to known function is the key to reveal its molecular principles with new challenges.

Micro-CT evaluation of microleakage under orthodontic ceramic brackets bonded with different bonding techniques and adhesives.

PubMed

Öztürk, Fırat; Ersöz, Mustafa; Öztürk, Seyit Ahmet; Hatunoğlu, Erdem; Malkoç, Sıddık

2016-04-01

The aim of this study was to evaluate microleakage under orthodontic ceramic brackets bonded with direct and different indirect bonding techniques and adhesives using micro-computed tomography. A total of 30 human maxillary premolars were randomly separated into five groups with six teeth in each group. In group I, teeth were bonded directly with Transbond XT (3M Unitek). In group II, group III, group IV, and group V, teeth were bonded through an indirect technique with Custom I.Q. (Reliance Orthodontic Products), Sondhi Rapid-Set (3M Unitek), RMbond (RMO), and Transbond IDB (3M Unitek), respectively, following the manufacturer's instructions. Micro-CT system model 1172 of Skyscan (Kontich, Belgium) was used to scan all samples. NRecon (Skyscan) version 1.6, CT-Analyser V.1.11 (Skyscan), and TView (SkyScan, Bvba) software programs were used for microleakage evaluation. Microleakage values between the test groups were assessed using the Kruskal-Wallis test, while the Wilcoxon signed rank test was used for within-group comparisons. The level of significance was set at P < 0.05. According to the Kruskal-Wallis analysis of variance test, there were no significant differences among the tested groups, with regard to volume and percentage (microleakage/region of interest × 100) of microleakage values (P < 0.05). The Wilcoxon signed rank test showed that coronal microleakage volume and percentage values significantly differed for RMbond and Transbond IDB groups. In the study, only ceramic brackets were used and microleakage into mini gaps did not show up on the micro-CT image because 50% silver nitrate solution could not penetrate into mini gaps which are smaller than silver nitrate particles. Use of direct and indirect bonding techniques with different adhesives did not significantly affect the amount of microleakage. © The Author 2015. Published by Oxford University Press on behalf of the European Orthodontic Society. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Analysis of the strength of interfacial hydrogen bonds between tubulin dimers using quantum theory of atoms in molecules.

PubMed

Ayoub, Ahmed T; Craddock, Travis J A; Klobukowski, Mariusz; Tuszynski, Jack

2014-08-05

Microtubules are key structural elements that, among numerous biological functions, maintain the cytoskeleton of the cell and have a major role in cell division, which makes them important cancer chemotherapy targets. Understanding the energy balance that brings tubulin dimers, the building blocks of microtubules, together to form a microtubule is especially important for revealing the mechanism of their dynamic instability. Several studies have been conducted to estimate various contributions to the free energy of microtubule formation. However, the hydrogen-bond contribution was not studied before as a separate component. In this work, we use concepts such as the quantum theory of atoms in molecules to estimate the per-residue strength of hydrogen bonds contributing to the overall stability that brings subunits together in pair of tubulin heterodimers, across both the longitudinal and lateral interfaces. Our study shows that hydrogen bonding plays a major role in the stability of tubulin systems. Several residues that are crucial to the binding of vinca alkaloids are shown to be strongly involved in longitudinal microtubule stabilization. This indicates a direct relation between the binding of these agents and the effect on the interfacial hydrogen-bonding network, and explains the mechanism of their action. Lateral contacts showed much higher stability than longitudinal ones (-462 ± 70 vs. -392 ± 59 kJ/mol), which suggests a dramatic lateral stabilization effect of the GTP cap in the β-subunit. The role of the M-loop in lateral stability in absence of taxol was shown to be minor. The B-lattice lateral hydrogen bonds are shown to be comparable in strength to the A-lattice ones (-462 ± 70 vs. -472 ± 46 kJ/mol). These findings establish the importance of hydrogen bonds to the stability of tubulin systems. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Studies on the regioselectivity and kinetics of the action of trypsin on proinsulin and its derivatives using mass spectrometry.

PubMed

Gardner, Qurra-tul-Ann Afza; Younas, Hooria; Akhtar, Muhammad

2013-01-01

Human M-proinsulin was cleaved by trypsin at the R(31)R(32)-E(33) and K(64)R(65)-G(66) bonds (B/C and C/A junctions), showing the same cleavage specificity as exhibited by prohormone convertases 1 and 2 respectively. Buffalo/bovine M-proinsulin was also cleaved by trypsin at the K(59)R(60)-G(61) bond but at the B/C junction cleavage occurred at the R(31)R(32)-E(33) as well as the R(31)-R(32)E(33) bond. Thus, the human isoform in the native state, with a 31 residue connecting C-peptide, seems to have a unique structure around the B/C and C/A junctions and cleavage at these sites is predominantly governed by the structure of the proinsulin itself. In the case of both the proinsulin species the cleavage at the B/C junction was preferred (65%) over that at the C/A junction (35%) supporting the earlier suggestion of the presence of some form of secondary structure at the C/A junction. Proinsulin and its derivatives, as natural substrates for trypsin, were used and mass spectrometric analysis showed that the k(cat.)/K(m) values for the cleavage were most favourable for the scission of the bonds at the two junctions (1.02±0.08×10(5)s(-1)M(-1)) and the cleavage of the K(29)-T(30) bond of M-insulin-RR (1.3±0.07×10(5)s(-1)M(-1)). However, the K(29)-T(30) bond in M-insulin, insulin as well as M-proinsulin was shielded from attack by trypsin (k(cat.)/K(m) values around 1000s(-1)M(-1)). Hence, as the biosynthetic path follows the sequence; proinsulin→insulin-RR→insulin, the K(29)-T(30) bond becomes shielded, exposed then shielded again respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Maternal bonding in childhood moderates autonomic responses to distress stimuli in adult males.

PubMed

Dalsant, Arianna; Truzzi, Anna; Setoh, Peipei; Esposito, Gianluca

2015-10-01

Mother-child bonding influences the development of cognitive and social skills. In this study we investigate how maternal attachment, developed in early childhood, modulates physiological responses to social stimuli later in life. Our results suggest that the autonomic nervous system's responses to vocal distress are moderated by the quality of participants' maternal bonding. In particular, participants with optimal maternal bonding showed a greater calming response to distressful stimuli whereas participants with non-optimal maternal bonding showed a heightened distress response. Copyright © 2015 Elsevier B.V. All rights reserved.

Resin-dentin bonds to EDTA-treated vs. acid-etched dentin using ethanol wet-bonding. Part II: Effects of mechanical cycling load on microtensile bond strengths.

PubMed

Sauro, Salvatore; Toledano, Manuel; Aguilera, Fatima Sánchez; Mannocci, Francesco; Pashley, David H; Tay, Franklin R; Watson, Timothy F; Osorio, Raquel

2011-06-01

To compare microtensile bond strengths (MTBS) subsequent to load cycling of resin bonded acid-etched or EDTA-treated dentin using a modified ethanol wet-bonding technique. Flat dentin surfaces were obtained from extracted human molars and conditioned using 37% H(3)PO(4) (PA) (15s) or 0.1M EDTA (60s). Five experimental adhesives and one commercial bonding agent were applied to the dentin and light-cured. Solvated experimental resins (50% ethanol/50% comonomers) were used as primers and their respective neat resins were used as the adhesives. The resin-bonded teeth were stored in distilled water (24h) or submitted to 5000 loading cycles of 90N. The bonded teeth were then sectioned in beams for MTBS. Modes of failure were examined by scanning electron microscopy. The most hydrophobic resin 1 gave the lowest bond strength values to both acid and EDTA-treated dentin. The hydrophobic resin 2 applied to EDTA-treated dentin showed lower bond strengths after cycling load but this did not occur when it was bonded to PA-etched dentin. Resins 3 and 4, which contained hydrophilic monomers, gave higher bond strengths to both EDTA-treated or acid-etched dentin and showed no significant difference after load cycling. The most hydrophilic resin 5 showed no significant difference in bond strengths after cycling loading when bonded to EDTA or phosphoric acid treated dentin but exhibited low bond strengths. The presence of different functional monomers influences the MTBS of the adhesive systems when submitted to cyclic loads. Adhesives containing hydrophilic comonomers are not affected by cycling load challenge especially when applied on EDTA-treated dentin followed by ethanol wet bonding. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Research and application of surface heat treatment for multipulse laser ablation of materials

NASA Astrophysics Data System (ADS)

Cai, Song; Chen, Genyu; Zhou, Cong

2015-11-01

This study analysed a laser ablation platform and built heat transfer equations for multipulse laser ablation of materials. The equations include three parts: laser emission after the material melt and gasification; end of laser emission after the material melts and there is the presence of a super-hot layer and solid-phase heat transfer changes during material ablation. For each of the three parts, the effects of evaporation, plasma shielding and energy accumulation under the pulse interval were considered. The equations are reasonable, and all the required parameters are only related to the laser parameters and material properties, allowing the model to have a certain versatility and practicability. The model was applied for numerical simulation of the heat transfer characteristics in the multipulse laser ablation of bronze and diamond. Next, experiments were conducted to analyse the topography of a bronze-bonded diamond grinding wheel after multipulse laser ablation. The theoretical analysis and experimental results showed that multipulse laser can merge the truing and dressing on a bronze-bonded diamond grinding wheel. This study provides theoretical guidance for optimising the process parameters in the laser ablation of a bronze-bonded diamond grinding wheel. A comparative analysis showed that the numerical solution to the model is in good agreement with the experimental data, thus verifying the correctness and feasibility of the heat transfer model.

Effect of Er,Cr:YSGG laser, air abrasion, and silane application on repaired shear bond strength of composites.

PubMed

Cho, S D; Rajitrangson, P; Matis, B A; Platt, J A

2013-01-01

Aged resin composites have a limited number of carbon-carbon double bonds to adhere to a new layer of resin. Study objectives were to 1) evaluate various surface treatments on repaired shear bond strength between aged and new resin composites and 2) to assess the influence of a silane coupling agent after surface treatments. Eighty disk-shape resin composite specimens were fabricated and thermocycled 5000 times prior to surface treatment. Specimens were randomly assigned to one of the three surface treatment groups (n=20): 1) air abrasion with 50-μm aluminum oxide, 2) tribochemical silica coating (CoJet), or 3) Er,Cr:YSGG (erbium, chromium: yttrium-scandium-gallium-garnet) laser or to a no-treatment control group (n=20). Specimens were etched with 35% phosphoric acid, rinsed, and dried. Each group was divided into two subgroups (n=10): A) no silanization and B) with silanization. The adhesive agent was applied and new resin composite was bonded to each conditioned surface. Shear bond strength was evaluated and data analyzed using two-way analysis of variance (ANOVA). Air abrasion with 50-μm aluminum oxide showed significantly higher repair bond strength than the Er,Cr:YSGG laser and control groups. Air abrasion with 50-μm aluminum oxide was not significantly different from tribochemical silica coating. Tribochemical silica coating had significantly higher repair bond strength than Er,Cr:YSGG laser and the control. Er,Cr:YSGG laser and the control did not have significantly different repair bond strengths. Silanization had no influence on repair bond strength for any of the surface treatment methods. Air abrasion with 50-μm aluminum oxide and tribochemical silica followed by the application of bonding agent provided the highest repair shear bond strength values, suggesting that they might be adequate methods to improve the quality of repairs of resin composites.

Casein phosphopeptide-amorphous calcium phosphate and shear bond strength of adhesives to primary teeth enamel.

PubMed

Farokh Gisovar, Elham; Hedayati, Nassim; Shadman, Niloofar; Shafiee, Leila

2015-02-01

CPP-ACP (Phosphopeptide-Amorphous Calcium Phosphate) has an important role in caries prevention in pediatric patients. This study was done, because of the great use of CPP-ACP and the need for restoration for teeth treated with CPP-ACP as well as the importance of shear bond strength of adhesives in the success of restorations. This study aimed to evaluate the effect of casein phosphopeptide-amorphous calcium phosphate (CPP-ACP) on shear bond strength of dental adhesives to enamel of primary teeth molars. This in vitro study was conducted on 180 extracted primary molars. They were randomly divided into 6 groups and each group was divided into 2 subgroups (treated with CPP-ACP and untreated). In subgroups with CPP-ACP, enamel was treated with CPP-ACP paste 1 h/d for 5 days. Types of adhesives that were evaluated in this study were Tetric N-Bond, AdheSE, AdheSE One F, single Bond 2, SE Bond, and Adper Prompt L-Pop. Shear bond strength was tested with a universal testing machine and mode of failure was evaluated under stereomicroscope. Data were analyzed by T test, 2-way analysis of variance (ANOVA), Tukey and Fisher exact test using SPSS18. P < 0.05 was considered as significance level. Shear bond strengths of different adhesive systems to enamel of primary teeth treated and untreated with CPP-ACP showed no significant difference (P > 0.05). Mode of failure in all groups regardless of CPP-ACP administration was mainly adhesive type. Our results indicated that CPP-ACP did not affect shear bond strength of studied adhesives to primary teeth enamel. To have a successful and durable composite restoration, having a high strength bonding is essential. Considering the wide use of CPP-ACP in preventing tooth decay and the role of adhesive shear bond strength (SBS) in success of composite restoration, we conducted the present study to evaluate the effect of CPP-ACP on the SBS of adhesives to primary teeth enamel.

Bonding and Integration Technologies for Silicon Carbide Based Injector Components

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay

2008-01-01

Advanced ceramic bonding and integration technologies play a critical role in the fabrication and application of silicon carbide based components for a number of aerospace and ground based applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. Ceramic to ceramic diffusion bonding and ceramic to metal brazing technologies are being developed for this injector application. For the diffusion bonding, titanium interlayers (PVD and foils) were used to aid in the joining of silicon carbide (SiC) substrates. The influence of such variables as surface finish, interlayer thickness (10, 20, and 50 microns), processing time and temperature, and cooling rates were investigated. Microprobe analysis was used to identify the phases in the bonded region. For bonds that were not fully reacted an intermediate phase, Ti5Si3Cx, formed that is thermally incompatible in its thermal expansion and caused thermal stresses and cracking during the processing cool-down. Thinner titanium interlayers and/or longer processing times resulted in stable and compatible phases that did not contribute to microcracking and resulted in an optimized microstructure. Tensile tests on the joined materials resulted in strengths of 13-28 MPa depending on the SiC substrate material. Non-destructive evaluation using ultrasonic immersion showed well formed bonds. For the joining technology of brazing Kovar fuel tubes to silicon carbide, preliminary development of the joining approach has begun. Various technical issues and requirements for the injector application are addressed.

Shear bond strengths of self-etching adhesives to caries-affected dentin on the gingival wall.

PubMed

Koyuturk, Alp Erdin; Sengun, Abdulkadir; Ozer, Fusun; Sener, Yagmur; Gokalp, Alparslan

2006-03-01

The purpose of this study was to evaluate the bonding ability of five current self-etching adhesives to caries-affected dentin on the gingival wall. Seventy extracted human molars with approximal dentin caries were employed in this study. In order to obtain caries-affected dentin on the gingival wall, grinding was performed under running water. Following which, specimens mounted in acrylic blocks and composite resins of the bonding systems were bonded to dentin with plastic rings and then debonded by shear bond strength. With Clearfil SE Bond, bonding to caries-affected dentin showed the highest bond strength. With Optibond Solo Plus Self-Etch, bonding to caries-affected dentin showed higher shear bond strength than AQ Bond, Tyrian SPE & One-Step Plus, and Prompt-L-Pop (p<0.05). Further, the bond strengths of Clearfil SE Bond and Optibond Solo Plus Self-Etch to sound dentin were higher than those of Prompt-L-Pop, AQ Bond, and Tyrian SPE & One-Step Plus (p<0.05). In conclusion, besides micromechanical interlocking through hybrid layer formation, bond strength of self-etch adhesives to dentin may be increased from additional chemical interaction between the functional monomer and residual hydroxyapatite. The results of this study confirmed that differences in bond strength among self-etching adhesives to both caries-affected and sound dentin were due to chemical composition rather than acidity.

Comparison of the Effect of Dentin Bonding, Dentin Sealing Agents on the Microleakage of Provisional Crowns Fabricated with Direct and Indirect Technique-An Invitro Study

PubMed Central

Muthukumar, B; Kumar, M Vasantha

2015-01-01

Background Postoperative sensitivity after temporization is a common complaint in Fixed Partial Denture patients. It is caused by weak and ill fitting temporary restorations which results in microleakage. This can be controlled by providing good temporary restorations and by coating the exposed dentinal tubules of the prepared tooth with dentin bonding agent or dental varnish. Aim The purpose of the study was to determine the effect of dentin-bonding, dentin sealing agents on the microleakage of temporary crowns made by tooth colored auto polymerizing resin fabricated with direct and indirect technique. Materials and Methods Thirty premolar and molar human teeth were collected which were extracted recently was used for the study. The teeth were marked and divided into 3 groups each containing 10 nos. They were individually mounted with self-cure acrylic resin. It was then mounted on a milling machine and crown preparations done. Temporary crowns were fabricated by direct and indirect method with two types of materials. In group A (Control group), the temporary crowns fabricated with both direct and indirect method were cemented directly with temporary luting cement. In group B dentine-bonding agent (solobond M) was applied once to the prepared surface of each tooth specimen before the cementation of temporary crowns where as in case of group C a single layer of dental varnish is applied prior to crown cementation. The entire specimens were immersed in 1% methylene blue and allowed to undergo thermal treatment. It was then sectioned in a hard tissue microtome. Each section was evaluated for dye penetration into the dentin tubules by comparing it with a visual scale. Statistical Analysis SPSS Version 13 software was used for non-parametric data analysis by a qualified statistician. P-values less than 0.05 (p-value<0.05) were considered to be statistically significant. Results Group B (Dentin Bonding Agent) specimens cemented with crowns fabricated in direct technique showed the least amount of microleakage when compared with group A and group C. Group C (Dental Varnish) specimen showed comparatively more amount of microleakage than that of group B. Group A (control group) specimens showed the maximum amount of microleakage. Conclusion The application of a single layer of Dental varnish appears to be of no significant benefit when compared to crowns cemented with the application of Dentin bonding agent on the tooth surface. The application of a single layer of Dentin bonding agent (Solobond M) and temporary crowns fabricated with direct technique may be of some benefit for crown preparations as an interim measure prior to the luting of final crown. PMID:26266219

Modified low-temperture direct bonding method for vacuum microelectronics application

NASA Astrophysics Data System (ADS)

Ju, Byeong-Kwon; Lee, Duck-Jung; Choi, Woo-Beom; Lee, Yun-Hi; Jang, Jin; Lee, Kwang-Bae; Oh, Myung-Hwan

1997-06-01

This paper presents the process and experimental results for the improved silicon-to-glass bonding using silicon direct bonding (SDB) followed by anodic bonding. The initial bonding between glass and silicon was caused by the hydrophilic surfaces of silicon-glass ensemble using SDB method. Then the initially bonded specimen had to be strongly bonded by anodic bonding process. The effects of the bonding process parameters on the interface energy were investigated as functions of the bonding temperature and voltage. We found that the specimen which was bonded using SDB process followed by anodic bonding process had higher interface energy than one using anodic bonding process only. The main factor contributing to the higher interface energy in the glass-to-silicon assemble bonded by SDB followed by anodic bonding was investigated by secondary ion mass spectroscopy analysis.

The influence of temporary cements on dental adhesive systems for luting cementation.

PubMed

Ribeiro, José C V; Coelho, Paulo G; Janal, Malvin N; Silva, Nelson R F A; Monteiro, André J; Fernandes, Carlos A O

2011-03-01

This study tested the hypothesis that bond strength of total- and self-etching adhesive systems to dentine is not affected by the presence of remnants from either eugenol-containing (EC) or eugenol-free (EF) temporary cements after standardized cleaning procedures. Thirty non-carious human third molars were polished flat to expose dentine surfaces. Provisional acrylic plates were fabricated and cemented either with EC, EF or no temporary cements. All specimens were incubated for 7 days in water at 37°C. The restorations were then taken out and the remnants of temporary cements were mechanically removed with a dental instrument. The dentine surfaces were cleaned with pumice and treated with either total-etching (TE) or self-etching (SE) dental adhesive systems. Atomic force microscopy was used to examine the presence of remnants of temporary cements before and after dentine cleaning procedures. Composite resin build-ups were fabricated and cemented to the bonded dentine surfaces with a resin luting cement. The specimens were then sectioned to obtain 0.9mm(2) beams for microtensile bond strength testing. Fractographic analysis was performed by optical and scanning electron microscopy. ANOVA showed lower mean microtensile bond strength in groups of specimens treated with EC temporary cement than in groups treated with either no cement or an EF cement (p<0.05). Mean microtensile bond strength was lower in groups employing the SE rather than the TE adhesive system (p<0.001). SE samples were also more likely to fail during initial processing of the samples. There was no evidence of interaction between cement and adhesive system effects on tensile strength. Fractographic analysis indicated different primary failure modes for SE and TE bonding systems, at the dentine-adhesive interface and at the resin cement-resin composite interface, respectively. The use of eugenol-containing temporary cements prior to indirect bonding restorations reduce, to a statistically similar extent, the bond strength of both total- and self-etching adhesive systems to dentine. Copyright © 2011 Elsevier Ltd. All rights reserved.

Influence of contamination on bonding to zirconia ceramic.

PubMed

Yang, Bin; Scharnberg, Michael; Wolfart, Stefan; Quaas, Anne C; Ludwig, Klaus; Adelung, Rainer; Kern, Matthias

2007-05-01

The purpose of this study was to investigate the influences of contaminations and cleaning methods on bonding to dental zirconia ceramic. After saliva immersion and using silicone disclosing agent, airborne-particle abraded ceramic specimens were cleaned with isopropanol (AL), acetone (AC), 37% phosphoric acid (PA), additional airborne-particle abrasion (AA), or only with water rinsing (SS). Airborne-particle abraded specimens without contaminations (CL) were used as control group. For chemical analysis specimens of all groups were examined with X-ray photoelectron spectroscopy (XPS). Plexiglas tubes filled with composite resin were bonded to ceramic specimens using a phosphate-monomer containing composite luting resin. After 3-day water storage, tensile bond strengths (TBS) were tested. XPS analysis of group SS showed the presence of saliva and silicone (Si) contamination on the surface. The ratios of carbon/zirconium and oxygen/zirconium for groups PA and AA were comparable to those ratios obtained for group CL, indicating the removal of the organic saliva contamination. Airborne-particle abrasion and acetone completely removed Si contamination from ceramic surfaces. Isopropanol had little cleaning effect on the two contaminants. TBS (median +/- standard deviation) in MPa of the groups SS (11.6 +/- 3.1), AL (10.0 +/- 2.9), and AC (13.0 +/- 2.8) were statistically lower than those of groups PA (33.6 +/- 5.5), AA (40.1 +/- 3.6), and CL (47.0 +/- 8.1) (p < 0.001), while no differences were found in TBS between groups AA and CL (p > 0.5). Contamination significantly reduced bond strengths to zirconia ceramic. Airborne-particle abrasion was the most effective cleaning method.

Supramolecular structures for determination and identification of the bond lengths in novel uranyl complexes from their infrared spectra

NASA Astrophysics Data System (ADS)

El-Sonbati, A. Z.; Diab, M. A.; Morgan, Sh. M.; Seyam, H. A.

2018-02-01

Novel dioxouranium (VI) heterochelates with neutral bidentate compounds (Ln) have been synthesized. The ligands and the heterochelates [UO2(Ln)2(O2NO)2] were confirmed and characterized by elemental analysis, 1H NMR, UV.-Vis, IR, mass spectroscopy, X-ray diffraction and thermogravimetric analysis (TGA). IR spectral data suggest that the molecules of the Schiff base are coordinated to the central uranium atom (ON donor). The nitrato groups are coordinated as bidentate ligands. The thermodynamic parameters were calculated using Coats-Redfern and Horowitz-Metzger methods. The ligands (Ln) and their complexes (1-3) showed the υ3 frequency of UO22+ has been shown to be an excellent molecular probe for studying the coordinating power of the ligands. The values of υ3 of the prepared complexes containing UO22+ were successfully used to calculate the force constant, FUO (1n 10-8N/Å) and the bond length RUO (Å) of the Usbnd O bond. A strategy based upon both theoretical and experimental investigations has been adopted. The theoretical aspects are described in terms of the well-known theory of 5d-4f transitions. Wilson's, matrix method, Badger's formula, and Jones and El-Sonbati equations were used to calculate the Usbnd O bond distances from the values of the stretching and interaction force constants. The most probable correlation between Usbnd O force constant to Usbnd O bond distance were satisfactorily discussed in term of Badger's rule and the equations suggested by Jones and El-Sonbati. The effect of Hammett's constant is also discussed.

19 CFR Appendix C to Part 113 - Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows

Code of Federal Regulations, 2014 CFR

2014-04-01

... for Sale at United States Boat Shows C Appendix C to Part 113 Customs Duties U.S. CUSTOMS AND BORDER... Appendix C to Part 113—Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows ____, as...

19 CFR Appendix C to Part 113 - Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows

Code of Federal Regulations, 2013 CFR

2013-04-01

... for Sale at United States Boat Shows C Appendix C to Part 113 Customs Duties U.S. CUSTOMS AND BORDER... Appendix C to Part 113—Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows ____, as...

19 CFR Appendix C to Part 113 - Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows

Code of Federal Regulations, 2012 CFR

2012-04-01

... for Sale at United States Boat Shows C Appendix C to Part 113 Customs Duties U.S. CUSTOMS AND BORDER... Appendix C to Part 113—Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows Bond for Deferral of Duty on Large Yachts Imported for Sale at United States Boat Shows ____, as...

Bonding temperature dependence of GaInAsP/InP laser diode grown on hydrophilically directly bonded InP/Si substrate

NASA Astrophysics Data System (ADS)

Aikawa, Masaki; Onuki, Yuya; Hayasaka, Natsuki; Nishiyama, Tetsuo; Kamada, Naoki; Han, Xu; Kallarasan Periyanayagam, Gandhi; Uchida, Kazuki; Sugiyama, Hirokazu; Shimomura, Kazuhiko

2018-02-01

The bonding-temperature-dependent lasing characteristics of 1.5 a µm GaInAsP laser diode (LD) grown on a directly bonded InP/Si substrate were successfully obtained. We have fabricated the InP/Si substrate using a direct hydrophilic wafer bonding technique at bonding temperatures of 350, 400, and 450 °C, and deposited GaInAsP/InP double heterostructure layers on this InP/Si substrate. The surface conditions, X-ray diffraction (XRD) analysis, photoluminescence (PL) spectra, and electrical characteristics after the growth were compared at these bonding temperatures. No significant differences were confirmed in X-ray diffraction analysis and PL spectra at these bonding temperatures. We realized the room-temperature lasing of the GaInAsP LD on the InP/Si substrate bonded at 350 and 400 °C. The threshold current densities were 4.65 kA/cm2 at 350 °C and 4.38 kA/cm2 at 400 °C. The electrical resistance was found to increase with annealing temperature.

Effect of various commercially available mouthrinses on shear bond strength of orthodontic metal brackets: an in vitro study.

PubMed

Meeran, Nazeer Ahmed; George, Ashwin Mathew

2013-01-01

Alcohol is known to degrade and dissolve the bisphenol A glycidyl methacrylate present in the composite resin. The effect of alcohol containing mouthrinses on the shear bond strength of orthodontic metal brackets bonded with composite resin has not been verified until date and is the purpose of this study. The aims and objectives of the present study were to evaluate (1) Whether there is a significant difference in the shear bond strength of metal orthodontic brackets after the 1 year (12 h) and 2 years simulation (24 h) of mouth rinsing with 4 different commercially available mouthrinses (2 alcoholic and 2 alcohol-free mouthrinses) when compared to the control. (2) Whether alcohol containing mouthrinses have more adverse effect on the shear bond strength when compared with alcohol-free mouthrinses. (3) To assess the site of bond failure using adhesive remnant index. Experimental - laboratory based. A total of 100 upper premolars extracted for orthodontic purpose were collected immediately after extraction, cleared soft-tissue debris and blood and immediately stored in distilled water with 0.1% thymol crystals added to inhibit bacterial growth. Two alcohol containing mouthrinses and two alcohol-free mouthrinses were used and the bonded teeth were placed in the mouthrinses for a stipulated period of time (1 year simulation and 2 years simulation) and shear bond strength were tested using Lloyd Universal Testing Machine. The data were analyzed using analysis of variance and paired samples t-test. After the 1 year and 2 years simulation time, samples stored in alcohol containing mouthrinses showed lower bond strength (P < 0.05) when compared to samples stored in alcohol free mouthrinses and distilled water (control). Alcohol containing mouthrinses affect the shear bond strength of the metal orthodontic brackets bonded with composite resin (Transbond XT in the present study), more when compared with alcohol-free mouthrinses. It is, therefore, highly advisable to avoid alcohol containing mouthrinses in patients undergoing orthodontic treatment and use alcohol-free mouthrinses as adjuncts to regular oral hygiene procedures for maintaining good enamel integrity and periodontal health, without compromising the shear bond strength of the bonded metal brackets.

Development and Characterization of the Bonding and Integration Technologies Needed for Fabricating Silicon Carbide Based Injector Components

NASA Technical Reports Server (NTRS)

Halbig,Michael C.; Singh, Mrityunjay

2008-01-01

Advanced ceramic bonding and integration technologies play a critical role in the fabrication and application of silicon carbide based components for a number of aerospace and ground based applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. Ceramic to ceramic diffusion bonding and ceramic to metal brazing technologies are being developed for this injector application. For the diffusion bonding technology, titanium interlayers (coatings and foils) were used to aid in the joining of silicon carbide (SiC) substrates. The influence of such variables as surface finish, interlayer thickness, and processing time were investigated. Electron microprobe analysis was used to identify the reaction formed phases. In the diffusion bonds, an intermediate phase, Ti5Si3Cx, formed that is thermally incompatible in its thermal expansion and caused thermal stresses and cracking during the processing cool-down. Thinner interlayers of pure titanium and/or longer processing times resulted in an optimized microstructure. Tensile tests on the joined materials resulted in strengths of 13-28 MPa depending on the SiC substrate material. Nondestructive evaluation using ultrasonic immersion showed well formed bonds. For the joining technology of brazing Kovar fuel tubes to silicon carbide, preliminary development of the joining approach has begun. Various technical issues and requirements for the injector application are addressed.

Dimerization of the keto tautomer of acetohydroxamic acid—infrared matrix isolation and theoretical study

NASA Astrophysics Data System (ADS)

Sałdyka, Magdalena; Mielke, Zofia

2005-05-01

Dimerization of the keto tautomer of acetohydroxamic acid has been studied using FTIR matrix isolation spectroscopy and DFT(B3LYP)/6-31+G(d,p) calculations. Analysis of CH 3CONHOH/Ar matrix spectra indicates formation of two dimers in which two intramolecular CO···H sbnd ON bonds within two interacting acetohydroxamic acid molecules are retained. A chain dimer I is stabilized by the intermolecular CO···H sbnd N hydrogen bond, whereas the cyclic dimer II is stabilized by two intermolecular N sbnd H···O(H)N bonds. Twelve vibrations were identified for dimer I and six vibrations for dimer II; the observed frequency shifts show a good agreement with the calculated ones for the structures I and II. Both dimers have comparable binding energies ( ΔEZPECPI, II = -7.02, -6.34 kcal mol -1) being less stable than calculated structures III and IV ( ΔEZPECPIII, IV = -9.50, -8.87 kcal mol -1) in which one or two intramolecular hydrogen bonds are disrupted. In the most stable 10-membered cyclic dimer III, two intermolecular CO···H sbnd ON hydrogen bonds are formed at expense of intramolecular hydrogen bonds of the same type. The formation of the less stable (AHA) 2 dimers in the studied matrixes indicates that the formation of (AHA) 2 is kinetically and not thermodynamically controlled.

Evaluation of shear bond strength of orthodontic brackets bonded with nano-filled composites.

PubMed

Chalipa, Javad; Akhondi, Mohammad Sadegh Ahmad; Arab, Sepideh; Kharrazifard, Mohammad Javad; Ahmadyar, Maryam

2013-09-01

The purpose of this study was to evaluate the shear bond strength (SBS) of orthodontic brackets bonded with two types of nano-composites in comparison to a conventional orthodontic composite. Sixty extracted human first premolars were randomly divided into 3 groups each containing 20 teeth. In group I, a conventional orthodontic composite (Transbond XT) was used to bond the brackets, while two nano-composites (Filtek TM Supreme XT and AELITE Aesthetic Enamel) were used in groups II and III respectively. The teeth were stored in distilled water at 37°C for 24 hours, thermocycled in distilled water and debonded with a universal testing machine at a crosshead speed of 1 mm/min. The adhesive remnant index (ARI) was also evaluated using a stereomicroscope. AELITE Aesthetic Enamel nano-composite revealed a SBS value of 8.44±2.09 MPa, which was higher than Transbond XT (6.91±2.13) and Filtek TM Supreme XT (6.04±2.01). Statistical analysis revealed a significant difference between groups II and III (P < 0.05). No significant difference was found between groups I and III, and between groups I and II (P > 0.05). Evaluation of ARI showed that Transbond XT left fewer adhesive remains on teeth after debonding. Results of this study indicate that the aforementioned nano-composites can be successfully used for bonding orthodontic brackets.

Intra- and intermolecular H-bond mediated tautomerization and dimerization of 3-methyl-1,2-cyclopentanedione: Infrared spectroscopy in argon matrix and CCl 4 solution

NASA Astrophysics Data System (ADS)

Samanta, Amit K.; Pandey, Prasenjit; Bandyopadhyay, Biman; Mukhopadhyay, Anamika; Chakraborty, Tapas

2011-05-01

Mid-infrared spectra of 3-methyl-1,2-cyclopentanedione (3-MeCPD) have been recorded by isolating the molecule in a cold argon matrix (8 K) and also in CCl 4 solution at room temperature. The spectral features reveal that in both media, the molecule exists exclusively in an enol tautomeric form, which is stabilized by an intramolecular O sbnd H⋯O hydrogen bond. NBO analysis shows that the preferred conformer is further stabilized because of hyperconjugation interaction between the methyl and vinyl group of the enol tautomer. In CCl 4 solution, the molecule undergoes extensive self association and generates a doubly hydrogen bonded centrosymmetric dimer. The dimerization constant ( K d) is estimated to have a value of ˜9 L mol -1 at room temperature (25 °C) and the thermodynamic parameters, Δ H°, Δ S° and Δ G°, of dimerization are estimated by measuring K d at several temperatures within the range 22-60 °C. The same dimer is also produced when the matrix is annealed at a higher temperature. In addition, a non-centrosymmetric singly hydrogen bonded dimer is also identified in the argon matrix. A comparison between the spectral features of the two dimers indicates that the dimerization effect on doubly H-bonded case is influenced by cooperative interaction between the two H-bonds.

Enamel microhardness and bond strengths of self-etching primer adhesives.

PubMed

Adebayo, Olabisi A; Burrow, Michael F; Tyas, Martin J; Adams, Geoffrey G; Collins, Marnie L

2010-04-01

The aim of this study was to determine the relationship between enamel surface microhardness and microshear bond strength (microSBS). Buccal and lingual mid-coronal enamel sections were prepared from 22 permanent human molars and divided into two groups, each comprising the buccal and lingual enamel from 11 teeth, to analyze two self-etching primer adhesives (Clearfil SE Bond and Tokuyama Bond Force). One-half of each enamel surface was tested using the Vickers hardness test with 10 indentations at 1 N and a 15-s dwell time. A hybrid resin composite was bonded to the other half of the enamel surface with the adhesive system assigned to the group. After 24 h of water storage of specimens at 37 degrees C, the microSBS test was carried out on a universal testing machine at a crosshead speed of 1 mm min(-1) until bond failure occurred. The mean microSBS was regressed on the mean Vickers hardness number (VHN) using a weighted regression analysis in order to explore the relationship between enamel hardness and microSBS. The weights used were the inverse of the variance of the microSBS means. Neither separate correlation analyses for each adhesive nor combined regression analyses showed a significant correlation between the VHN and the microSBS. These results suggest that the microSBS of the self-etch adhesive systems are not influenced by enamel surface microhardness.

Experimental and Numerical Study of the Influence of Substrate Surface Preparation on Adhesion Mechanisms of Aluminum Cold Spray Coatings on 300M Steel Substrates

NASA Astrophysics Data System (ADS)

Nastic, A.; Vijay, M.; Tieu, A.; Rahmati, S.; Jodoin, B.

2017-10-01

The effect of substrate surface topography on the creation of metallurgical bonds and mechanical anchoring points has been studied for the cold spray deposition of pure aluminum on 300M steel substrate material. The coatings adhesion strength showed a significant decrease from 31.0 ± 5.7 MPa on polished substrates to 6.9 ± 2.0 MPa for substrates with roughness of 2.2 ± 0.5 μm. Strengths in the vicinity of 45 MPa were reached for coatings deposited onto forced pulsed waterjet treated surfaces with roughnesses larger than 33.8 μm. Finite element analysis has confirmed the sole presence of mechanical anchoring in coating adhesion strength for all surface treatment except polished surfaces. Grit embedment has been shown to be non-detrimental to coating adhesion for the current deposited material combination. The particle deformation process during impacts has been studied through finite element analysis using the Preston-Tonks-Wallace (PTW) constitutive model. The obtained equivalent plastic strain (PEEQ), temperature, contact pressure and velocity vector were correlated to the particle ability to form metallurgical bonds. Favorable conditions for metallurgical bonding were found to be highest for particles deposited on polished substrates, as confirmed by fracture surface analysis.

Characterization of non-classical Csbnd Br⋯π interactions in (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene and related derivatives of ferrocene

NASA Astrophysics Data System (ADS)

Shukla, Rahul; Panini, Piyush; McAdam, C. John; Robinson, Brian H.; Simpson, Jim; Tagg, Tei; Chopra, Deepak

2017-03-01

Amongst the halogens, the involvement of bromine atoms in various types of intermolecular interactions is comparatively the least studied. In this manuscript, we report the formation of Csbnd Br⋯π interactions, with the π-rings being the cyclopentadienyl (Cp) rings of a ferrocene molecule in a newly synthesized compound (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene. We have also performed a detailed quantitative analysis on Csbnd Br⋯π interactions observed in the synthesized molecule and in several related molecules found in the Cambridge Structure Database (CSD) showing the presence of these interactions. A topological analysis based upon QTAIM theory and electrostatic potential ESP mapped on the Hirshfeld surface of these molecules confirm that these interactions are better described as "halogen bonds" wherein the electropositive region (σ-hole) on the Br-atom interacts with the electronegative region over the Cp-ring of the ferrocene. Further, the electronegative region on the bromine atom (perpendicular to the Csbnd Br bond) was observed to be involved in the formation of highly directional Csbnd H⋯Br interactions with the ∠Csbnd Br⋯H close to 90°. Thus the bromine atom is acting as both a "halogen bond donor" and "hydrogen bond acceptor" in the crystal packing with the two interactions being mutually orthogonal.

Synthesis, spectroscopic investigations (FT-IR, NMR, UV-Vis, and TD-DFT), and molecular docking of (E)-1-(benzo[d][1, 3]dioxol-6-yl)-3-(6-methoxynaphthalen-2-yl)prop-2-en-1-one

NASA Astrophysics Data System (ADS)

Therasa Alphonsa, A.; Loganathan, C.; Athavan Alias Anand, S.; Kabilan, S.

2017-02-01

The compound (E)-1-(benzo [d] [1, 3] dioxol-6-yl)-3-(6-methoxy naphthalen-2-yl) prop-2-en-1-one (AKN) was synthesized and characterized by FT-IR, NMR, and UV-Vis spectrometer. The optimized molecular geometry, bond lengths, bond angles, atomic charges, harmonic vibrational wave numbers and intensities of vibrational bonds of the title compound have been investigated by Time dependent- Density Functional Theory (TD-DFT) using a standard B3LYP method with 6-31 G (d, p) basis set available in the Gaussian 09W package. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge-independent atomic orbital method (GIAO). Experimental excitation energies of the molecules were matched with the theoretically calculated energies. The atomic charge distributions of the various atoms present in the AKN were obtained by Mulliken charge population analysis. The Molecular Electrostatic Potential (MEP) analysis reveals the sites for electrophilic attack and nucleophilic reactions in the molecule. The difference between the observed and scaled frequencies was small. The HOMO to LUMO transition implies an electron density transfer. The intramolecular contacts have been interpreted using Natural Bond Orbital (NBO) analysis. The calculation results were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. To provide information about the interactions between human cytochrome protein and the novel compound theoretically, docking studies were carried out using Schrödinger software.

Pair bond formation leads to a sustained increase in global cerebral glucose metabolism in monogamous male titi monkeys (Callicebus cupreus).

PubMed

Maninger, Nicole; Hinde, Katie; Mendoza, Sally P; Mason, William A; Larke, Rebecca H; Ragen, Benjamin J; Jarcho, Michael R; Cherry, Simon R; Rowland, Douglas J; Ferrer, Emilio; Bales, Karen L

2017-04-21

Social bonds, especially attachment relationships, are crucial to our health and happiness. However, what we know about the neural substrates of these bonds is almost exclusively limited to rodent models and correlational experiments in humans. Here, we used socially monogamous non-human primates, titi monkeys (Callicebus cupreus) to experimentally examine changes in regional and global cerebral glucose metabolism (GCGM) during the formation and maintenance of pair bonds. Baseline positron emission tomography (PET) scans were taken of thirteen unpaired male titi monkeys. Seven males were then experimentally paired with females, scanned and compared, after one week, to six age-matched control males. Five of the six control males were then also paired and scanned after one week. Scans were repeated on all males after four months of pairing. PET scans were coregistered with structural magnetic resonance imaging (MRI), and region of interest (ROI) analysis was carried out. A primary finding was that paired males showed a significant increase in [ 18 F]-fluorodeoxyglucose (FDG) uptake in whole brain following one week of pairing, which is maintained out to four months. Dopaminergic, "motivational" areas and those involved in social behavior showed the greatest change in glucose uptake. In contrast, control areas changed only marginally more than GCGM. These findings confirm the large effects of social bonds on GCGM. They also suggest that more studies should examine how social manipulations affect whole-brain FDG uptake, as opposed to assuming that it does not change across condition. Copyright © 2017 IBRO. Published by Elsevier Ltd. All rights reserved.

Unimolecular rearrangement of the simplest compound models with a selenium-oxygen, selenium-sulphur and selenium-selenium bond: SeXH and HSeXH (X = O,S,Se)

NASA Astrophysics Data System (ADS)

Viana, Rommel B.

2017-04-01

The aim of this study was to characterise the simplest compound models with a selenium-oxygen, selenium-sulphur and selenium-selenium bond as the SeXH and HSeXH isomers (X = O,S,Se). One of the main aspects of this investigation was to provide a description on the isomerisation pathways involving 2[H,Se,X] and 1[2H,Se,X] potential energy surfaces calculated at the CCSD(T)/CBS//MP2/cc-pVTZ level. The energy difference was 13 kcal mol-1 between hydroxyselenide (SeOH) and oxoselenium (HSeO), while a gap of 3 kcal mol-1 was predicted between thiol-selenide (SeSH) and selenol-sulphide (HSeS). The SeOH→HSeO unimolecular rearrangement showed a barrier energy of 44.6 kcal mol-1, decreasing almost two times in sulphur and selenium analogous reactions. In addition, hydroxyselenide (HSeOH), thioselenenic acid (HSeSH) and diselane (HSeSeH) were the global minimum configurations in the ground state, while the energy differences among the other isomers were close to 30 kcal mol-1. The HSeXH→H2SeX and HSeXH→SeXH2 isomerisations showed barrier energies ranging from 40 to 65 kcal mol-1, while these reverse routes presented heights that were three times smaller. The kinetic rate constant of each 1,2-H shift reaction was performed here as well as an analysis of the selenium-chalcogen bonds using natural bond orbital and bond order index methodologies.

Surface modification for bonding between amalgam and orthodontic brackets.

PubMed

Wongsamut, Wittawat; Satrawaha, Sirichom; Wayakanon, Kornchanok

2017-01-01

Testing of methods to enhance the shear bond strength (SBS) between orthodontic metal brackets and amalgam by sandblasting and different primers. Three hundred samples of amalgam restorations (KerrAlloy ® ) were prepared in self-cured acrylic blocks, polished, and divided into two groups: nonsandblasted and sandblasted. Each group was divided into five subgroups with different primers used in surface treatment methods, with a control group of bonded brackets on human mandibular incisors. Following the surface treatments, mandibular incisor brackets (Unitek ® ) were bonded on the amalgam with adhesive resin (Transbond XT ® ). The SBS of the samples was tested. The adhesive remnant index (ARI) and failure modes were then determined under a stereo-microscope. Two-way analysis of variance, Chi-square, and Kruskal-Wallis tests were performed to calculate the correlations between and among the SBS and ARI values, the failure modes, and surface roughness results. There were statistically significant differences of SBS among the different adhesive primers and sandblasting methods ( P < 0.05). The sandblasted amalgam with Assure Plus ® showed the highest SBS ( P < 0.001). Samples mainly showed an ARI score = 1 and mix-mode failure. There was a statistically significant difference of surface roughness between nonsandblasted amalgam and sandblasted amalgam ( P < 0.05), but no significant differences among priming agents ( P > 0.05). Using adhesive primers with sandblasting together effectively enhances the SBS between orthodontic metal brackets and amalgam. The two primers with the ingredient methacryloxydecyl dihydrogen phosphate (MDP) monomer, Alloy Primer ® and Assure Plus ® , were the most effective. Including sandblasting in the treatment is essential to achieve the bonding strength required.

Structures of aspartic acid-96 in the L and N intermediates of bacteriorhodopsin: analysis by Fourier transform infrared spectroscopy

NASA Technical Reports Server (NTRS)

Maeda, A.; Sasaki, J.; Shichida, Y.; Yoshizawa, T.; Chang, M.; Ni, B.; Needleman, R.; Lanyi, J. K.

1992-01-01

The light-induced difference Fourier transform infrared spectrum between the L or N intermediate minus light-adapted bacteriorhodopsin (BR) was measured in order to examine the protonated states and the changes in the interactions of carboxylic acids of Asp-96 and Asp-115 in these intermediates. Vibrational bands due to the protonated and unprotonated carboxylic acid were identified by isotope shift and band depletion upon substitution of Asp-96 or -115 by asparagine. While the signal due to the deprotonation of Asp-96 was clearly observed in the N intermediate, this residue remained protonated in L. Asp-115 was partially deprotonated in L. The C = O stretching vibration of protonated Asp-96 of L showed almost no shift upon 2H2O substitution, in contrast to the corresponding band of Asp-96 or Asp-115 of BR, which shifted by 9-12 cm-1 under the same conditions. In the model system of acetic acid in organic solvents, such an absence of the shift of the C = O stretching vibration of the protonated carboxylic acid upon 2H2O substitution was seen only when the O-H of acetic acid is hydrogen-bonded. The non-hydrogen-bonded monomer showed the 2H2O-dependent shift. Thus, the O-H bond of Asp-96 enters into hydrogen bonding upon conversion of BR to L. Its increased hydrogen bonding in L is consistent with the observed downshift of the O-H stretching vibration of the carboxylic acid of Asp-96.

Pair bond Formation Leads to a Sustained Increase in Global Cerebral Glucose Metabolism in Monogamous Male Titi Monkeys (Callicebus cupreus)

PubMed Central

Maninger, Nicole; Hinde, Katie; Mendoza, Sally P.; Mason, William A.; Larke, Rebecca H.; Ragen, Benjamin J; Jarcho, Michael R.; Cherry, Simon R.; Rowland, Douglas J.; Ferrer, Emilio; Bales, Karen L.

2017-01-01

Social bonds, especially attachment relationships, are crucial to our health and happiness. However, what we know about the neural substrates of these bonds is almost exclusively limited to rodent models and correlational experiments in humans. Here, we used socially monogamous non-human primates, titi monkeys (Callicebus cupreus) to experimentally examine changes in regional and global cerebral glucose metabolism during the formation and maintenance of pair bonds. Baseline positron emission tomography (PET) scans were taken of thirteen unpaired male titi monkeys. Seven males were then experimentally paired with females, scanned and compared, after one week, to six age-matched control males. Five of the six control males were then also paired and scanned after one week. Scans were repeated on all males after four months of pairing. PET scans were coregistered with structural magnetic resonance imaging (MRI), and region of interest (ROI) analysis was carried out. A primary finding was that paired males showed a significant increase in FDG uptake in whole brain following one week of pairing, which is maintained out to four months. Dopaminergic, “motivational” areas and those involved in social behavior showed the greatest change in glucose uptake. In contrast, control areas changed only marginally more than GCGM. These findings confirm the large effects of social bonds on global cerebral glucose metabolism. They also suggest that more studies should examine how social manipulations affect whole brain FDG uptake, as opposed to assuming that it does not change across condition. PMID:28242440

State of the science of maternal-infant bonding: a principle-based concept analysis.

PubMed

Bicking Kinsey, Cara; Hupcey, Judith E

2013-12-01

to provide a principle-based analysis of the concept of maternal-infant bonding. principle-based method of concept analysis for which the data set included 44 articles published in the last decade from Pubmed, CINAHL, and PyschINFO/PsychARTICLES. literature inclusion criteria were English language, articles published in the last decade, peer-reviewed journal articles and commentary on published work, and human populations. after a brief review of the history of maternal-infant bonding, a principle-based concept analysis was completed to examine the state of the science with regard to this concept. The concept was critically examined according to the clarity of definition (epistemological principle), applicability of the concept (pragmatic principle), consistency in use and meaning (linguistic principle), and differentiation of the concept from related concepts (logical principle). Analysis of the concept revealed: (1) Maternal-infant bonding describes maternal feelings and emotions towards her infant. Evidence that the concept encompasses behavioural or biological components was limited. (2) The concept is clearly operationalised in the affective domain. (3) Maternal-infant bonding is linguistically confused with attachment, although the boundaries between the concepts are clearly delineated. despite widespread use of the concept, maternal-infant bonding is at times superficially developed and subject to confusion with related concepts. Concept clarification is warranted. A theoretical definition of the concept of maternal-infant bonding was developed to aid in the clarification, but more research is necessary to further clarify and advance the concept. nurse midwives and other practitioners should use the theoretical definition of maternal-infant bonding as a preliminary guide to identification and understanding of the concept in clinical practice. Copyright © 2013 Elsevier Ltd. All rights reserved.

STATE OF THE SCIENCE OF MATERNAL-INFANT BONDING: A PRINCIPLE-BASED CONCEPT ANALYSIS

PubMed Central

Bicking Kinsey, Cara; Hupcey, Judith E.

2013-01-01

Objective To provide a principle-based analysis of the concept of maternal-infant bonding. Design Principle-based method of concept analysis for which the data set included 44 articles published in the last decade from Pubmed, CINAHL, and PyschINFO/PsychARTICLES. Setting Literature inclusion criteria were English language, articles published in the last decade, peer-reviewed journal articles and commentary on published work, and human populations. Measurement and Findings After brief review of the history of maternal-infant bonding, a principle-based concept analysis was completed to examine the state of the science with regard to this concept. The concept was critically examined according to the clarity of definition (epistemological principle), applicability of the concept (pragmatic principle), consistency in use and meaning (linguistic principle), and differentiation of the concept from related concepts (logical principle). Analysis of the concept revealed: (1) maternal-infant bonding describes maternal feelings and emotions towards her infant. Evidence that the concept encompasses behavioral or biological components was limited; (2) the concept is clearly operationalized in the affective domain; and (3) maternal-infant bonding is linguistically confused with attachment, although the boundaries between the concepts are clearly delineated. Key Conclusion Despite widespread use of the concept, maternal-infant bonding is at times superficially developed and subject to confusion with related concepts. Concept clarification is warranted. A theoretical definition of the concept of maternal-infant bonding was developed to aid in the clarification, but more research is necessary to further clarify and advance the concept. Implications for Practice Nurse midwives and other practitioners should use the theoretical definition of maternal-infant bonding as a preliminary guide to identification and understanding of the concept in clinical practice. PMID:23452661

Home Runs and Humbugs: Comment on Bond and DePaulo (2008)

ERIC Educational Resources Information Center

O'Sullivan, Maureen

2008-01-01

In 2006, C. F. Bond Jr. and B. M. DePaulo provided a meta-analysis of means and concluded that average lie detection accuracy was significantly greater than chance for most people. Now, they have presented an analysis of standard deviations (C. F. Bond Jr. & B. M. DePaulo, 2008), claiming that there are no reliable individual differences in lie…

Oxygen termination of homoepitaxial diamond surface by ozone and chemical methods: An experimental and theoretical perspective

NASA Astrophysics Data System (ADS)

Navas, Javier; Araujo, Daniel; Piñero, José Carlos; Sánchez-Coronilla, Antonio; Blanco, Eduardo; Villar, Pilar; Alcántara, Rodrigo; Montserrat, Josep; Florentin, Matthieu; Eon, David; Pernot, Julien

2018-03-01

Phenomena related with the diamond surface of both power electronic and biosensor devices govern their global behaviour. In particular H- or O-terminations lead to wide variations in their characteristics. To study the origins of such aspects in greater depth, different methods to achieve oxygen terminated diamond were investigated following a multi-technique approach. DFT calculations were then performed to understand the different configurations between the C and O atoms. Three methods for O-terminating the diamond surface were performed: two physical methods with ozone at different pressures, and an acid chemical treatment. X-ray photoelectron spectroscopy, spectroscopic ellipsometry, HRTEM, and EELS were used to characterize the oxygenated surface. Periodic-DFT calculations were undertaken to understand the effect of the different ways in which the oxygen atoms are bonded to carbon atoms on the diamond surface. XPS results showed the presence of hydroxyl or ether groups, composed of simple Csbnd O bonds, and the acid treatment resulted in the highest amount of O on the diamond surface. In turn, ellipsometry showed that the different treatments led to the surface having different optical properties, such as a greater refraction index and extinction coefficient in the case of the sample subjected to acid treatment. TEM analysis showed that applying temperature treatment improved the distribution of the oxygen atoms at the interface and that this generates a thinner amount of oxygen at each position and higher interfacial coverage. Finally, DFT calculations showed both an increase in the number of preferential electron transport pathways when π bonds and ether groups appear in the system, and also the presence of states in the middle of the band gap when there are π bonds, Cdbnd C or Cdbnd O.

Investigation of charge-transfer hydrogen bonding interaction of 1-(2-pyridylazo)-2-naphthol (PAN) and 4-(2-Pyridylazo)resorcinol (PAR) with chloranilic acid through experimental and DFT studies

NASA Astrophysics Data System (ADS)

Karmakar, Animesh; Singh, Bula

2018-07-01

The H-bonding interaction of 1-(2-pyridylazo)-2-naphthol (PAN) and 4-(2-Pyridylazo) resorcinol (PAR) with chloranilic acid (CLA) have been considered spectroscopically in methanol solvent. PAN and PAR were used as a ligand and this two ligands has diverse application in spectrophotometric, chelatometric analysis of different metal ions. However, it is seen as of the literature analysis that no molecular complex of PAN and PAR with CLA was reported. The creation of charge-transfer H-bonded adduct gives a outlook to progress the physico-chemical scenery of the donor. So the complex of PAN and PAR with chloranilic acid was recounted in this work in methanol medium. Both the hydrogen-bonded molecular complexes have been prepared and identified using 1H NMR, FT-IR, and elemental analysis. Spectroscopic data point out that PAN and PAR discretely interact with CLA by a physically potent H-bonding interaction. The thermal constancy of the above molecular complexes has been determined by TGA-DTA analysis. The computational calculation also supported the development of the H-bonded charge-transfer adduct.

Interest rate next-day variation prediction based on hybrid feedforward neural network, particle swarm optimization, and multiresolution techniques

NASA Astrophysics Data System (ADS)

Lahmiri, Salim

2016-02-01

Multiresolution analysis techniques including continuous wavelet transform, empirical mode decomposition, and variational mode decomposition are tested in the context of interest rate next-day variation prediction. In particular, multiresolution analysis techniques are used to decompose interest rate actual variation and feedforward neural network for training and prediction. Particle swarm optimization technique is adopted to optimize its initial weights. For comparison purpose, autoregressive moving average model, random walk process and the naive model are used as main reference models. In order to show the feasibility of the presented hybrid models that combine multiresolution analysis techniques and feedforward neural network optimized by particle swarm optimization, we used a set of six illustrative interest rates; including Moody's seasoned Aaa corporate bond yield, Moody's seasoned Baa corporate bond yield, 3-Month, 6-Month and 1-Year treasury bills, and effective federal fund rate. The forecasting results show that all multiresolution-based prediction systems outperform the conventional reference models on the criteria of mean absolute error, mean absolute deviation, and root mean-squared error. Therefore, it is advantageous to adopt hybrid multiresolution techniques and soft computing models to forecast interest rate daily variations as they provide good forecasting performance.

Rhodium clustering process on defective (8,0) SWCNT: Analysis of chemical and physical properties using density functional theory

NASA Astrophysics Data System (ADS)

Ambrusi, Ruben E.; Luna, C. Romina; Sandoval, Mario G.; Bechthold, Pablo; Pronsato, M. Estela; Juan, Alfredo

2017-12-01

The Spin-polarized density functional theory is used to study the effect of a single vacancy in a (8,0) single-walled carbon nanotube (SWCNT) on the Rh clustering process. The vacancy is considered oxygenated and non-oxygenated and, in each case, different Rhn cluster sizes (n = 1-4) are taken into account. For the analysis of these systems some physical and chemical properties are calculated, such as binding energy (Eb), work function (WF), magnetic moment, charge transfer, bond length, band gap (Eg), and density of state (DOS). From this analysis it can be concluded that: a single Rh atom and Rh2 dimer are adsorbed on vacancy without oxygen, whereas Rh3 and Rh4 clusters prefer to be adsorbed on oxygenated vacancy. In all cases, Rh adsorption induces a magnetic moment. When the Rh atom and Rh2 dimer are bonded to the defective SWCNT, it has been found that they show a semiconductor behavior that could be interesting to use in the spintronic area. In the case of Rh3 and Rh4 clusters our results show a metallic behavior suggesting that these systems are good candidates for nanotube contact.

From Common Sense Concepts to Scientifically Conditioned Concepts of Chemical Bonding: An Historical and Textbook Approach Designed to Address Learning and Teaching Issues at the Secondary School Level

NASA Astrophysics Data System (ADS)

Croft, Michael; de Berg, Kevin

2014-09-01

This paper selects six key alternative conceptions identified in the literature on student understandings of chemical bonding and illustrates how a historical analysis and a textbook analysis can inform these conceptions and lead to recommendations for improving the teaching and learning of chemical bonding at the secondary school level. The historical analysis and the textbook analysis focus on the concepts of charge, octet, electron pair, ionic, covalent and metallic bonding. Finally, a table of recommendations is made for teacher and student in the light of four fundamental questions and the six alternative conceptions to enhance the quality of the curriculum resources available and the level of student engagement.

Determination of apparent coupling factors for adhesive bonded acrylic plates using SEAL approach

NASA Astrophysics Data System (ADS)

Pankaj, Achuthan. C.; Shivaprasad, M. V.; Murigendrappa, S. M.

2018-04-01

Apparent coupling loss factors (CLF) and velocity responses has been computed for two lap joined adhesive bonded plates using finite element and experimental statistical energy analysis like approach. A finite element model of the plates has been created using ANSYS software. The statistical energy parameters have been computed using the velocity responses obtained from a harmonic forced excitation analysis. Experiments have been carried out for two different cases of adhesive bonded joints and the results have been compared with the apparent coupling factors and velocity responses obtained from finite element analysis. The results obtained from the studies signify the importance of modeling of adhesive bonded joints in computation of the apparent coupling factors and its further use in computation of energies and velocity responses using statistical energy analysis like approach.

Microtensile Bond Strength of Embrace Wetbond Hydrophilic Sealant in Different Moisture Contamination: An In-Vitro Study.

PubMed

Panigrahi, Antarmayee; Srilatha, K T; Panigrahi, Rajat G; Mohanty, Susant; Bhuyan, Sanat K; Bardhan, Debojyoti

2015-07-01

Contamination of etched enamel with saliva has been shown to result in sealant failure. Recently, a hydrophilic sealant has been introduced. In absence of documented literature, this in vitro study was undertaken to ascertain the efficacy of Embrace Wet Bond without reduction of microtensile bond strength in the different moisture contamination. A 5mm block of sealant were built over prepared occlusal surface of 40 non-carious therapeutically extracted third molars which were sectioned into 1mm thick stick and tested using Zwick micro tensile tester. Obtained data were subjected to descriptive analysis, one-way ANOVA and Scheffe's post-hoc tests. Mean microtensile bond strength of Embrace sealant was not significantly lowered in different moisture contamination groups except Group 3 (air drying), which showed very highly significant (p<0.001) decrease in μTBS as compared to Group 1 (non-contaminated). Mean μTBS of Embrace sealant remains largely unchanged even in presence of moisture. Owing to its hydrophilic property, this sealant can be a great help in cases where maintaining isolation is difficult.

[The Relationships among Perceived Parental Bonding, Illness Perception, and Anxiety in Adult Patients with Congenital Heart Diseases].

PubMed

Shin, Nayeon; Jang, Youha; Kang, Younhee

2017-04-01

The purposes of this study were to identify the relationships among perceived parental bonding, illness perception, and anxiety and to determine the influences of perceived parental bonding and illness perception on anxiety in adult patients with congenital heart diseases. In this study a descriptive correlational design with survey method was utilized. The participants were 143 adult patients with congenital heart disease being cared for in the cardiology out-patient clinic of A medical center. Data were collected using the Parental Bonding Instrument, Illness Perception Questionnaire Revised Scale, and Cardiac Anxiety Questionnaire Scale. Data were analyzed using descriptive statistics, independent t-test, one-way ANOVA, Pearson correlation analysis, and hierarchial regression analyses. There showed significant positive relationships of anxiety with maternal overprotection, consequences, and personal control respectively. Among predictors, maternal overprotection (β=.45), consequence (β=.26), and personal control (β=-.03) had statistically significant influence on anxiety. Nursing interventions to decrease maternal overprotection and negative consequence, and to enhance personal control are essential to decrease the anxiety of adult patients with congenital heart diseases. © 2017 Korean Society of Nursing Science

Fluorescence from Multiple Chromophore Hydrogen-Bonding States in the Far-Red Protein TagRFP675.

PubMed

Konold, Patrick E; Yoon, Eunjin; Lee, Junghwa; Allen, Samantha L; Chapagain, Prem P; Gerstman, Bernard S; Regmi, Chola K; Piatkevich, Kiryl D; Verkhusha, Vladislav V; Joo, Taiha; Jimenez, Ralph

2016-08-04

Far-red fluorescent proteins are critical for in vivo imaging applications, but the relative importance of structure versus dynamics in generating large Stokes-shifted emission is unclear. The unusually red-shifted emission of TagRFP675, a derivative of mKate, has been attributed to the multiple hydrogen bonds with the chromophore N-acylimine carbonyl. We characterized TagRFP675 and point mutants designed to perturb these hydrogen bonds with spectrally resolved transient grating and time-resolved fluorescence (TRF) spectroscopies supported by molecular dynamics simulations. TRF results for TagRFP675 and the mKate/M41Q variant show picosecond time scale red-shifts followed by nanosecond time blue-shifts. Global analysis of the TRF spectra reveals spectrally distinct emitting states that do not interconvert during the S1 lifetime. These dynamics originate from photoexcitation of a mixed ground-state population of acylimine hydrogen bond conformers. Strategically tuning the chromophore environment in TagRFP675 might stabilize the most red-shifted conformation and result in a variant with a larger Stokes shift.

Copper diffusion and mechanical toughness at Cu-silica interfaces glued with polyelectrolyte nanolayers

NASA Astrophysics Data System (ADS)

Gandhi, D. D.; Singh, A. P.; Lane, M.; Eizenberg, M.; Ramanath, G.

2007-04-01

We demonstrate the use of polyallylamine hydrochloride (PAH)-polystyrene sulfonate (PSS) nanolayers to block Cu transport into silica. Cu/PSS-PAH/SiO2 structures show fourfold enhancement in device failure times during bias thermal annealing at 200 °C at an applied electric field of 2 MV/cm, when compared with structures with pristine Cu-SiO2 interfaces. Although the bonding at both Cu-PSS and PAH-SiO2 interfaces are strong, the interfacial toughness measured by the four-point bend tests is ˜2 Jm-2. Spectroscopic analysis of fracture surfaces reveals that weak electrostatic bonding at the PSS-PAH interface is responsible for the low toughness. Similar behavior is observed for Cu-SiO2 interfaces modified with other polyelectrolyte bilayers that inhibit Cu diffusion. Thus, while strong bonding at Cu-barrier and barrier-dielectric interfaces may be sufficient for blocking copper transport across polyelectrolyte bilayers, strong interlayer molecular bonding is a necessary condition for interface toughening. These findings are of importance for harnessing MNLs for use in future device wiring applications.

The Effect of Temperature on Faceplate/Core Delamination in Composite/Titanium Sandwich Plates

NASA Technical Reports Server (NTRS)

Liechti, Kenneth M.; Marton, Balazs

2000-01-01

A study was made of the delamination behavior of sandwich beams made of titanium core bonded to face-plates that consisted of carbon fiber reinforced polymer composite. Nominally mode I behavior was considered at 23C and 180C, by making use of a specially reinforced double cantilever (DCB) specimens. The toughness of the bond between the faceplate and the core was determined on the basis of a beam on elastic foundation analysis. The specimen compliance, and toughness were all independent of temperature in these relatively short-term experiments. The fracture mechanism showed temperature dependence, due to the hygrothermal sensitivity of the adhesive.

Direct folding simulation of a long helix in explicit water

NASA Astrophysics Data System (ADS)

Gao, Ya; Lu, Xiaoliang; Duan, Lili; Zhang, Dawei; Mei, Ye; Zhang, John Z. H.

2013-05-01

A recently proposed Polarizable Hydrogen Bond (PHB) method has been employed to simulate the folding of a 53 amino acid helix (PDB ID 2KHK) in explicit water. Under PHB simulation, starting from a fully extended structure, the peptide folds into the native state as confirmed by measured time evolutions of radius of gyration, root mean square deviation (RMSD), and native hydrogen bond. Free energy and cluster analysis show that the folded helix is thermally stable under the PHB model. Comparison of simulation results under, respectively, PHB and standard nonpolarizable force field demonstrates that polarization is critical for stable folding of this long α-helix.

Nature of non-nuclear (3, -3) π-attractor and π-bonding: Theoretical analysis on π-electron density

NASA Astrophysics Data System (ADS)

Lv, Jiao; Yang, Lihua; Sun, Zheng; Meng, Lingpeng; Li, Xiaoyan

2018-01-01

Understanding the nature of π-electron density is important to characterize the conjugate π molecular systems. In this work, the π-electron densities of some typical conjugated π molecular systems were separated from their total electron densities; the positions and natures of non-nuclear (3, -3) π-attractors and the π-bond critical points (π-BCPs) are investigated. The calculated results show that for the same element, the position of the π-attractor is constant, regardless of the chemical surroundings. The position of the π-BCP is closer to the atom with the larger electronegativity.

FTIR cryospectroscopic and ab initio studies of desflurane-dimethyl ether H-bonded complexes.

PubMed

Melikova, S M; Rutkowski, K S; Rospenk, M

2017-09-05

The IR spectra of mixtures of desflurane and dimethyl ether are studied with the help of FTIR cryospectroscopy in liquefied Kr at T~118-158K. Comparative analysis of the experimental data and results of ab initio calculations show that either of the two C-H groups of desflurane is involved in heterodimer formation of comparable strengths. The blue frequency shift is found for stretching vibrations of those C-H donors which directly participate in H-bond formation. Additionally the complexes are stabilized by weaker contacts between hydrogen atoms of dimethyl ether and fluorine atoms of desflurane. Copyright © 2017 Elsevier B.V. All rights reserved.

Density functional theory studies on molecular structure and vibrational spectra of NLO crystal L-phenylalanine phenylalanium nitrate for THz application

NASA Astrophysics Data System (ADS)

Amalanathan, M.; Hubert Joe, I.; Rastogi, V. K.

2011-12-01

Molecular structure, FT-IR and Raman spectra of L-phenylalanine phenylalanium nitrate have been investigated using density functional theory calculation. The polarizability and hyperpolarizability value of the crystal is also calculated. Natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction. Simultaneous activation of ring C sbnd C stretching modes shows the non-centrosymmetric symmetry. Terahertz time-domain spectroscopy has been used to detect the absorption spectra in the frequency range from 0.05 to 1.3 THz. Theoretically predicted β value exhibits the high nonlinear optical activity.

Evaluation of the Shear Bond Strength of Composite Resin to Wet and Dry Enamel Using Dentin Bonding Agents Containing Various Solvents.

PubMed

Usha, Carounanidy; Ramarao, Sathyanarayanan; John, Bindu Meera; Rajesh, Praveen; Swatha, S

2017-01-01

Bonding of composite resin to dentin mandates a wet substrate whereas, enamel should be dry. This may not be easily achievable in intracoronal preparations where enamel and dentin are closely placed to each other. Therefore, Dentin Bonding Agents (DBA) are recommended for enamel and dentinal bonding, where enamel is also left moist. A research question was raised if the "enamel-only" preparations will also benefit from wet enamel bonding and contemporary DBA. The aim of this study was to compare the shear bond strengths of composite resin, bonded to dry and wet enamel using fifth generation DBA (etch and rinse system) containing various solvents such as ethanol/water, acetone and ethanol. The crowns of 120 maxillary premolars were split into buccal and lingual halves. They were randomly allocated into four groups of DBA: Group 1-water/ethanol based, Group 2-acetone based, Group 3-ethanol based, Group 4-universal bonding agent (control group). The buccal halves and lingual halves were bonded using the wet bonding and dry bonding technique respectively. After application of the DBAs and composite resin build up, shear bond strength testing was done. Group 1 (ethanol/water based ESPE 3M, Adper Single Bond) showed highest bond strength of (23.15 MPa) in dry enamel. Group 2 (acetone based Denstply, Prime and Bond NT, showed equal bond strength in wet and dry enamel condition (18.87 MPa and 18.02 MPa respectively). Dry enamel bonding and ethanol/water based etch and rinse DBA can be recommended for "enamel-only" tooth preparations.

Structure and Bonding in CE5- (E=Al-Tl) Clusters: Planar Tetracoordinate Carbon versus Pentacoordinate Carbon.

PubMed

Ravell, Estefanía; Jalife, Said; Barroso, Jorge; Orozco-Ic, Mesías; Hernández-Juárez, Gerardo; Ortiz-Chi, Filiberto; Pan, Sudip; Cabellos, José Luis; Merino, Gabriel

2018-03-24

The structure, bonding, and stability of clusters with the empirical formula CE 5 - (E=Al-Tl) have been analyzed by means of high-level computations. The results indicate that, whereas aluminum and gallium clusters have C 2v structures with a planar tetracoordinate carbon (ptC), their heavier homologues prefer three-dimensional C 4v forms with a pentacoordinate carbon center over the ptC one. The reason for such a preference is a delicate balance between the interaction energy of the fifth E atom with CE 4 and the distortion energy. Moreover, bonding analysis shows that the ptC systems can be better described as CE 4 - , with 17-valence electrons interacting with E. The ptC core in these systems exhibits double aromatic (both σ and π) behavior, but the σ contribution is dominating. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new approach to construct a fused 2-ylidene chromene ring: highly regioselective synthesis of novel chromeno quinoxalines.

PubMed

Kumar, K Shiva; Rambabu, D; Prasad, Bagineni; Mujahid, Mohammad; Krishna, G Rama; Rao, M V Basaveswara; Reddy, C Malla; Vanaja, G R; Kalle, Arunasree M; Pal, Manojit

2012-06-28

Regioselective construction of a fused 2-ylidene chromene ring was achieved for the first time by using AlCl(3)-induced C-C bond formation followed by Pd/C-Cu mediate coupling-cyclization strategy. A number of chromeno[4,3-b]quinoxaline derivatives were prepared by using this strategy. Single crystal X-ray diffraction study of a representative compound e.g. 6-(2,2-dimethylpropylidene)-4-methyl-6H-chromeno[4,3-b]quinoxalin-3-ol confirmed the presence of an exocyclic C-C double bond with Z-geometry. The crystal structure analysis and hydrogen bonding patterns of the same compound along with its structure elaboration via propargylation followed by Sonogashira coupling of the resulting terminal alkyne is presented. A probable mechanism for the formation of 2-ylidene chromene ring is discussed. Some of the compounds synthesized showed anticancer properties when tested in vitro.

Decarboxylation of furfural on Pd(111): Ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Xue, Wenhua; Dang, Hongli; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2013-03-01

Furfural conversion over metal catalysts plays an important role in the studies of biomass-derived feedstocks. We report ab initio molecular dynamics simulations for the decarboxylation process of furfural on the palladium surface at finite temperatures. We observed and analyzed the atomic-scale dynamics of furfural on the Pd(111) surface and the fluctuations of the bondlengths between the atoms in furfural. We found that the dominant bonding structure is the parallel structure in which the furfural plane, while slightly distorted, is parallel to the Pd surface. Analysis of the bondlength fluctuations indicates that the C-H bond is the aldehyde group of a furfural molecule is likely to be broken first, while the C =O bond has a tendency to be isolated as CO. Our results show that the reaction of decarbonylation dominates, consistent with the experimental measurements. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSEDE's and NERSC's supercomputers.

Theoretical study of interactions between cysteine and perfluoropropanoic acid in gas and aqueous phase

NASA Astrophysics Data System (ADS)

Holmes, Tiffani M.; Doskocz, Jacek; Wright, Terrance; Hill, Glake A.

The interaction of perfluoropropanoic acid (PFPA) with the amino acid cysteine was investigated using density functional theory. Previous studies suggest that the peroxisome proliferator chemical, perfluorooctanoic acid, is circulated throughout the body by way of sulfur-containing amino acids. We present conformational analysis of the interactions of PFPA, a small model of perfluorooctanoic acid, with the sulfur-containing amino acid which occur by the process of hydrogen bonding, in which the hydrogen of the sulfhydryl group interacts with the carboxyl oxygen, and the amino nitrogen forms a hydrogen bond with the hydrogen of the bond OH group of the fluorinated alkyl. We also show in our structures a recently characterized weak nonbonded interaction between divalent sulfur and a main chain carboxyl oxygen in proteins. B3LYP calculated free energies and interaction energies predict low-energy, high-interaction conformations for complex systems of perfluorinated fatty acid interactions with cysteine.

[EARLY MOTHER-CHILD BONDING FACTORS ASSOCIATED WITH CHILDREN OBESITY].

PubMed

Vargas Martínez, Gabriela; Cruzat Mandich, Claudia; Díaz Castrillón, Fernanda; Moore Infante, Catalina; Ulloa Jiménez, Valentina

2015-11-01

The aim of this study is to describe the experience of a group of mothers with obese children, regarding how early bond affects the relationship that both have with food and this, in turn, impacts on childhood obesity. The present study has a qualitative, exploratory and descriptive design. The sample consists of five chilean women between 22 and 39 years old, with obese children between 2 and 4 years old. In-depth interviews were carried out and open coding strategy was used as method of analysis. Results show a tendency of mothers to establish insecure attachment relations, difficulties of tuning and expression of affection, and a predominance of a permissive parenting style around food. This has important implications for prevention and treatment of obesity, focusing on the attachment bond between mother and child. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.

Systematic reviews: I. The correlation between laboratory tests on marginal quality and bond strength. II. The correlation between marginal quality and clinical outcome.

PubMed

Heintze, Siegward D

2007-01-01

An accepted principle in restorative dentistry states that restorations should be placed with the best marginal quality possible to avoid postoperative sensitivity, marginal discoloration, and secondary caries. Different laboratory methods claim to predict the clinical performance of restorative materials, for example, tests of bond strength and microleakage and gap analysis. The purpose of this review was twofold: (1) find studies that correlated the results of bond strength tests with either microleakage or gap analysis for the same materials, and (2) find studies that correlated the results of microleakage and/or gaps with the clinical parameters for the same materials. Furthermore, influencing factors on the results of the laboratory tests were reviewed and assessed. For the first question, searches for studies were conducted in the MEDLINE database and IADR/AADR abtracts online with specific search and inclusion criteria. The outcome for each study was assessed on the basis of the statistical test applied in the study, and finally the number of studies with or without correlation was compiled. For the second question, results of the quantitative marginal analysis of Class V restorations published by the University of Zürich with the same test protocol and prospective clinical trials were searched that investigated the same materials for at least 2 years in Class V cavities. Pearson correlation coefficients were calculated for pooled data of materials and clinical outcome parameters such as retention loss, marginal discoloration, marginal integrity, and secondary caries. For the correlation of dye penetration and clinical outcome, studies on Class V restorations published by the same research institute were searched in MEDLINE that examined the same adhesive systems as the selected clinical trials. For the correlation bond strength/microleakage, 30 studies were included into the review, and for the correlation bond strength/gap analysis 18 studies. For both topics, about 80% of the studies revealed that there was no correlation between the two methods. For the correlation quantitative marginal analysis/clinical outcome, data were compared to the clinical outcome of 11 selected clinical studies. In only 2 out of the 11 studies (18%) did the clinical outcome match the prognosis based on the laboratory tests; the remaining studies did not show any correlation. When pooling data on 20 adhesive systems, no correlation was found between the percentage of continuous margin of restorations placed in extracted premolars and the percentage of teeth that showed no retention loss in clinical studies, no discoloured margins, acceptable margins, or absence of secondary caries. With regard to the correlation of dye penetration and clinical studies, no sufficient number of studies was found that matched the inclusion criteria. However, literature data suggest that there is no correlation between microleakage data as measured in the laboratory and clinical parameters. The results of bond strength tests did not correlate with laboratory tests that evaluated the marginal seal of restorations such as microleakage or gap analysis. The quantitative marginal analysis of Class V fillings in the laboratory was unable to predict the performance of the same materials in vivo. Therefore, microleakage tests or the quantitative marginal analysis should be abandoned and research should focus on laboratory tests that are validated with regard to their ability to satisfactorily predict the clinical performance of restorative materials.

Contact and Length Dependent Effects in Single-Molecule Electronics

NASA Astrophysics Data System (ADS)

Hines, Thomas

Understanding charge transport in single molecules covalently bonded to electrodes is a fundamental goal in the field of molecular electronics. In the past decade, it has become possible to measure charge transport on the single-molecule level using the STM break junction method. Measurements on the single-molecule level shed light on charge transport phenomena which would otherwise be obfuscated by ensemble measurements of groups of molecules. This thesis will discuss three projects carried out using STM break junction. In the first project, the transition between two different charge transport mechanisms is reported in a set of molecular wires. The shortest wires show highly length dependent and temperature invariant conductance behavior, whereas the longer wires show weakly length dependent and temperature dependent behavior. This trend is consistent with a model whereby conduction occurs by coherent tunneling in the shortest wires and by incoherent hopping in the longer wires. Measurements are supported with calculations and the evolution of the molecular junction during the pulling process is investigated. The second project reports controlling the formation of single-molecule junctions by means of electrochemically reducing two axial-diazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in-situ between the molecule and gold electrodes. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond. Finally, the third project investigates the role that molecular conformation plays in the conductance of oligothiophene single-molecule junctions. Ethyl substituted oligothiophenes were measured and found to exhibit temperature dependent conductance and transition voltage for molecules with between two and six repeat units. While the molecule with only one repeat unit shows temperature invariant behavior. Density functional theory calculations show that at higher temperatures the oligomers with multiple repeat units assume a more planar conformation, which increases the conjugation length and decreases the effective energy barrier of the junction.

Thermal analysis of a diffusion bonded Er3+,Yb3+:glass/Co2+: MgAl2O4 microchip lasers

NASA Astrophysics Data System (ADS)

Belghachem, Nabil; Mlynczak, Jaroslaw; Kopczynski, krzysztof; Mierczyk, Zygmunt; Gawron, Michal

2016-10-01

The analysis of thermal effects in a diffusion bonded Er3+,Yb3+:glass/Co2+:MgAl2O4 microchip laser is presented. The analysis is performed for both wavelengths at 940 nm and at 975 nm as well as for two different sides of pumping, glass side and saturable absorber side. The heat sink effect of Co2+:MgAl2O4, as well as the impact of the thermal expansion and induced stress on the diffusion bonding are emphasised. The best configurations for reducing the temperature peaks, the Von Mises stresses on the diffusion bonding, and the thermal lensing are determined.

Sc20C60: a volleyballene

NASA Astrophysics Data System (ADS)

Wang, Jing; Ma, Hong-Man; Liu, Ying

2016-06-01

An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable.An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable. Electronic supplementary information (ESI) available: Sc20C60: a Volleyballene_SI. See DOI: 10.1039/c5nr07784b

Effect of ambient vibration on solid rocket motor grain and propellant/liner bonding interface

NASA Astrophysics Data System (ADS)

Cao, Yijun; Huang, Weidong; Li, Jinfei

2017-05-01

In order to study the condition of structural integrity in the process of the solid propellant motor launching and transporting, the stress and strain field analysis were studied on a certain type of solid propellant motor. the vibration acceleration on the solid propellant motors' transport process were monitored, then the original vibration data was eliminated the noise and the trend term efficiently, finally the characteristic frequency of vibration was got to the finite element analysis. Experiment and simulation results show that the monitored solid propellant motor mainly bear 0.2 HZ and 15 HZ low frequency vibration in the process of transportation; Under the low frequency vibration loading, solid propellant motor grain stress concentration position is respectively below the head and tail of the propellant/liner bonding surface and the grain roots.

Inhibition of epidermal growth factor receptor by ferulic acid and 4-vinylguaiacol in human breast cancer cells.

PubMed

Sudhagar, S; Sathya, S; Anuradha, R; Gokulapriya, G; Geetharani, Y; Lakshmi, B S

2018-02-01

To examine the potential of ferulic acid and 4-vinylguaiacol for inhibiting epidermal growth factor receptor (EGFR) in human breast cancer cells in vitro. Ferulic acid and 4-vinylguaiacol limit the EGF (epidermal growth factor)-induced breast cancer proliferation and new DNA synthesis. Western blot analysis revealed both ferulic acid and 4-vinylguaiacol exhibit sustained inhibition of EGFR activation through down-regulation of Tyr 1068 autophosphorylation. Molecular docking analysis shows ferulic acid forming hydrogen bond interaction with Lys 745 and Met 793 whereas, 4-vinylguaiacol forms two hydrogen bonds with Phe 856 and exhibits stronger hydrophobic interactions with multiple amino acid residues at the EGFR kinase domain. Ferulic acid and 4-vinylguaiacol could serve as a potential structure for the development of new small molecule therapeutics against EGFR.

A Comprehensive Analysis in Terms of Molecule-Intrinsic, Quasi-Atomic Orbitals. III. The Covalent Bonding Structure of Urea.

PubMed

West, Aaron C; Schmidt, Michael W; Gordon, Mark S; Ruedenberg, Klaus

2015-10-15

The analysis of molecular electron density matrices in terms of quasi-atomic orbitals, which was developed in previous investigations, is quantitatively exemplified by a detailed application to the urea molecule. The analysis is found to identify strong and weak covalent bonding interactions as well as intramolecular charge transfers. It yields a qualitative as well as quantitative ab initio description of the bonding structure of this molecule, which raises questions regarding some traditional rationalizations.

The effects of dentin and intaglio indirect ceramic optimized polymer restoration surface treatment on the shear bond strength of resin cement

NASA Astrophysics Data System (ADS)

Puspitarini, A.; Suprastiwi, E.; Usman, M.

2017-08-01

Ceramic optimized polymer (ceromer) bonds to the tooth substrate through resin cements. The bond strength between dentin, resin cement, and ceromer depends on the applied surface treatment. To analyze the effects of dentin and intaglio ceromer surface treatment on the shear bond strength self-adhesive resin cement. Forty-five dentin premolar and ceromer specimens were bonded with resin cement and divided into three groups as follows: in group 1, no treatment was applied; in group 2, dentin surface treatment was carried out with acid etching and a bonding agent; and in group 3, dentin surface treatment was carried out with acid etching, a bonding agent, and intaglio ceromer surface treatment with etching and silane. All specimens were incubated at 37 °C for 24 hours, and the shear bond strength was measured using a universal testing machine. Group 3 showed the highest shear bond strength, followed by group 2. The surface treatment of dentin and intaglio ceromer showed significantly improved shear bond strength in the group comparison. Dentin and intaglio ceromer surface treatment can improved the shear bond strength self-adhesive resin cement.

Bond-based bilinear indices for computational discovery of novel trypanosomicidal drug-like compounds through virtual screening.

PubMed

Castillo-Garit, Juan Alberto; del Toro-Cortés, Oremia; Vega, Maria C; Rolón, Miriam; Rojas de Arias, Antonieta; Casañola-Martin, Gerardo M; Escario, José A; Gómez-Barrio, Alicia; Marrero-Ponce, Yovani; Torrens, Francisco; Abad, Concepción

2015-01-01

Two-dimensional bond-based bilinear indices and linear discriminant analysis are used in this report to perform a quantitative structure-activity relationship study to identify new trypanosomicidal compounds. A data set of 440 organic chemicals, 143 with antitrypanosomal activity and 297 having other clinical uses, is used to develop the theoretical models. Two discriminant models, computed using bond-based bilinear indices, are developed and both show accuracies higher than 86% for training and test sets. The stochastic model correctly indentifies nine out of eleven compounds of a set of organic chemicals obtained from our synthetic collaborators. The in vitro antitrypanosomal activity of this set against epimastigote forms of Trypanosoma cruzi is assayed. Both models show a good agreement between theoretical predictions and experimental results. Three compounds showed IC50 values for epimastigote elimination (AE) lower than 50 μM, while for the benznidazole the IC50 = 54.7 μM which was used as reference compound. The value of IC50 for cytotoxicity of these compounds is at least 5 times greater than their value of IC50 for AE. Finally, we can say that, the present algorithm constitutes a step forward in the search for efficient ways of discovering new antitrypanosomal compounds. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Diffusion Bonding of Silicon Carbide Ceramics using Titanium Interlayers

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay; Shpargel, Tarah P.; Kiser, James D.

2006-01-01

Robust joining approaches for silicon carbide ceramics are critically needed to fabricate leak free joints with high temperature mechanical capability. In this study, titanium foils and physical vapor deposited (PVD) titanium coatings were used to form diffusion bonds between SiC ceramics using hot pressing. Silicon carbide substrate materials used for bonding include sintered SiC and two types of CVD SiC. Microscopy results show the formation of well adhered diffusion bonds. The bond strengths as determined from pull tests are on the order of several ksi, which is much higher than required for a proposed application. Microprobe results show the distribution of silicon, carbon, titanium, and other minor elements across the diffusion bond. Compositions of several phases formed in the joint region were identified. Potential issues of material compatibility and optimal bond formation will also be discussed.

19 CFR 113.75 - Bond conditions for deferral of duty on large yachts imported for sale at United States boat shows.

Code of Federal Regulations, 2010 CFR

2010-04-01

... yachts imported for sale at United States boat shows. 113.75 Section 113.75 Customs Duties U.S. CUSTOMS... Customs Bond Conditions § 113.75 Bond conditions for deferral of duty on large yachts imported for sale at....C. 1484b for a dutiable large yacht imported for sale at a United States boat show must conform to...

19 CFR 113.75 - Bond conditions for deferral of duty on large yachts imported for sale at United States boat shows.

Code of Federal Regulations, 2011 CFR

2011-04-01

... yachts imported for sale at United States boat shows. 113.75 Section 113.75 Customs Duties U.S. CUSTOMS... Customs Bond Conditions § 113.75 Bond conditions for deferral of duty on large yachts imported for sale at....C. 1484b for a dutiable large yacht imported for sale at a United States boat show must conform to...

Effect of ultrasonic tip and root-end filling material on bond strength.

PubMed

Vivan, Rodrigo Ricci; Guerreiro-Tanomaru, Juliane Maria; Bernardes, Ricardo Affonso; Reis, José Mauricio Santos Nunes; Hungaro Duarte, Marco Antonio; Tanomaru-Filho, Mário

2016-11-01

The objective of this study was to evaluate the bond strength of three root-end filling materials (MTAA-MTA Angelus, MTAS-experimental MTA Sealer, and ZOE- zinc oxide and eugenol cement) in retrograde preparations performed with different ultrasonic tips (CVD, Trinity, and Satelec). Ninety 2-mm root sections from single-rooted human teeth were used. The retrograde cavities were prepared by using the ultrasonic tips, coupled to a device for position standardization. The specimens were randomly divided into nine groups: CVD MTAA; CVD MTAS; CVD ZOE; Trinity MTAA; Trinity MTAS; Trinity ZOE; Satelec MTAA; Satelec MTAS; Satelec ZOE. Each resin disc/dentin/root-end filling material was placed in the machine to perform the push-out test. The specimens were examined in a stereomicroscope to evaluate the type of failure. Data were submitted to statistical analysis using ANOVA and Tukey tests (α = 0.05). The highest bond strength was observed for the CVD tip irrespective of the material used (P < 0.05). There was no significant difference for the Trinity TU-18 diamond and S12 Satelec tips (P > 0.05). MTAA and MTAS showed highest bond strength. The most common type of failure was adhesion between the filling material and dentin wall, except for ZOE, where mixed failure was predominant. The CVD tip favored higher bond strength of the root-end filling materials. MTA Angelus and experimental MTAS presented bond strength to dentin prepared with ultrasonic tips. Root-end preparation with the CVD tip positively influences the bond strength of root-end filling materials. MTA Angelus and experimental MTAS present bond strength to be used as root-end filling materials.

A novel dentin bond strength measurement technique using a composite disk in diametral compression.

PubMed

Huang, Shih-Hao; Lin, Lian-Shan; Rudney, Joel; Jones, Rob; Aparicio, Conrado; Lin, Chun-Pin; Fok, Alex

2012-04-01

New methods are needed that can predict the clinical failure of dental restorations that primarily rely on dentin bonding. Existing methods have shortcomings, e.g. severe deviation in the actual stress distribution from theory and a large standard deviation in the measured bond strength. We introduce here a novel test specimen by examining an endodontic model for dentin bonding. Specifically, we evaluated the feasibility of using the modified Brazilian disk test to measure the post-dentin interfacial bond strength. Four groups of resin composite disks which contained a slice of dentin with or without an intracanal post in the center were tested under diametral compression until fracture. Advanced nondestructive examination and imaging techniques in the form of acoustic emission (AE) and digital image correlation (DIC) were used innovatively to capture the fracture process in real time. DIC showed strain concentration first appearing at one of the lateral sides of the post-dentin interface. The appearance of the interfacial strain concentration also coincided with the first AE signal detected. Utilizing both the experimental data and finite-element analysis, the bond/tensile strengths were calculated to be: 11.2 MPa (fiber posts), 12.9 MPa (metal posts), 8.9 MPa (direct resin fillings) and 82.6 MPa for dentin. We have thus established the feasibility of using the composite disk in diametral compression to measure the bond strength between intracanal posts and dentin. The new method has the advantages of simpler specimen preparation, no premature failure, more consistent failure mode and smaller variations in the calculated bond strength. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.